Release agent composition for light irradiation stripping and adhesive composition for light irradiation stripping

Abstract

The invention relates to a stripping agent composition or an adhesive composition, which is a stripping agent composition for light irradiation stripping or an adhesive composition for light irradiation stripping. The release agent composition or the adhesive composition contains a novolac resin having at least any of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, an epoxy resin containing a siloxane skeleton, and a solvent.

Description

Technical Field

[0001] The present invention relates to a release agent composition for photoirradiation release, an adhesive composition for photoirradiation release, a laminate, and a method for manufacturing a processed semiconductor substrate or an electronic device layer. Background Art

[0002] Regarding a semiconductor wafer obtained by integrating in a two-dimensional planar direction in the past, for the purpose of further integration, a semiconductor integration technology that integrates the plane further in the three-dimensional direction (lamination) is pursued. This three-dimensional lamination is a technology in which multiple layers are integrated while wiring through a through-silicon via (TSV). When integrating into multiple layers, each wafer to be integrated is thinned on the side opposite to the formed circuit surface (i.e., the back surface) by grinding, and the thinned semiconductor wafers are laminated.

[0003] Before thinning, a semiconductor wafer (also simply referred to as a wafer here) is bonded to a support for grinding using a grinding device. The bonding at this time must be easily releasable after grinding, so it is called temporary bonding. This temporary bonding must be easily disassembled from the support. When a large force is applied to the disassembly, sometimes the thinned semiconductor wafer is cut or deformed, and in order not to cause such a situation, it is easily disassembled. However, when grinding the back surface of the semiconductor wafer, it comes off or shifts due to grinding stress, which is not preferable. Therefore, the performance pursued by temporary bonding is to withstand the stress during grinding and be easily disassembled after grinding.

[0004] For example, the following performance is pursued: high stress (strong adhesive force) in the planar direction during grinding, and low stress (weak adhesive force) in the longitudinal direction during disassembly.

[0005] For such bonding and separation processes, a method using laser irradiation has been disclosed (for example, refer to Patent Documents 1 and 2), but with the further progress in the semiconductor field in recent years, new technologies related to release achieved by irradiation with light such as lasers have always been sought.

[0006] The present applicant has proposed a laminate that has an intermediate layer that can be releasably bonded between a support and a workpiece and is used for processing the workpiece. The intermediate layer at least includes a release layer that contacts the support side, and the release layer includes a novolak resin that deteriorates by absorbing light with a wavelength of 190 nm to 600 nm irradiated through the support (refer to Patent Document 3).

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004 - 64040

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2012-106486

[0011] Patent Document 3: Pamphlet of International Publication No. 2019 / 088103 SUMMARY OF THE INVENTION

[0012] Problems to be Solved by the Invention

[0013] In the method of peeling by light irradiation, after processing a semiconductor substrate such as a semiconductor wafer, the release agent layer is deteriorated by light irradiation, and the semiconductor substrate is easily peeled from the support substrate. Sometimes, foreign substances such as an adhesive layer, a release agent layer, and residues thereof adhere to the surfaces of the peeled semiconductor substrate and / or the support substrate, so the semiconductor substrate and / or the support substrate is cleaned. However, depending on the type of the release agent layer, it is sometimes difficult to remove foreign substances on the semiconductor substrate and the support substrate, and the cleaning becomes difficult.

[0014] In addition, according to the technique of Patent Document 3, the release agent layer is deteriorated by light irradiation, and the semiconductor substrate is easily peeled from the support substrate.

[0015] However, there has been no research on deteriorating the adhesive layer by light irradiation to easily peel the semiconductor substrate from the support substrate. In addition, depending on the type of the adhesive layer, it is sometimes difficult to remove foreign substances on the semiconductor substrate and the support substrate, and the cleaning becomes difficult.

[0016] The present invention has been completed in view of the above circumstances, and an object thereof is to provide a release agent composition for light irradiation peeling, a laminate using the release agent composition, and a method for manufacturing a processed semiconductor substrate or an electronic device layer, the release agent composition for light irradiation peeling being capable of forming a release agent layer having excellent releasability and excellent cleanability.

[0017] In addition, the present invention has been completed in view of the above circumstances, and an object thereof is to provide an adhesive composition for light irradiation peeling, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or an electronic device layer, the adhesive composition for light irradiation peeling being capable of forming an adhesive layer having excellent releasability and excellent cleanability.

[0018] Means for Solving the Problems

[0019] The present inventors have conducted intensive studies to solve the above technical problems, and as a result, have found that the above technical problems can be solved, and have completed the present invention having the following gist.

[0020] That is, the present invention includes the following.

[0021] [1] A stripper composition or an adhesive composition, which is a stripper composition for photoirradiation peeling or an adhesive composition for photoirradiation peeling, and the stripper composition or the adhesive composition contains: a novolak resin having at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, an epoxy resin containing a siloxane skeleton, and a solvent.

[0022] [2] The stripper composition or the adhesive composition according to [1], wherein the novolak resin contains at least any one of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3).

[0023]

[0024] (In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom.

[0025] C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain; or represents a methylene group.

[0026] C 3 represents a group derived from an aliphatic polycyclic compound.

[0027] C 4 represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0028] C 5 represents a single bond or a group having a structure derived from styrene.

[0029] In formula (C1-1), at least any one of C 1 , C 2 , and C 5 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0030] In formula (C1-2), at least any one of C 1 , C 3 , and C 5 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0031] In formula (C1-3), at least any one of C 2 , C 4 , and C 5at least any one of them has at least any group of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.)

[0032] [3] The stripper composition or adhesive composition according to [2], wherein the novolak resin contains at least any structural unit of the structural unit represented by the following formula (C1-1-1) and the structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1).

[0033]

[0034] (In formula (C1-1-1) and formula (C1-1-2), R 901 and R 902 represent substituents substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.)

[0035] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.)

[0036] R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group.)

[0037] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.)

[0038] R 904 The group of and R 905 The groups of optionally bond to each other to form a divalent group.)

[0039] Ar 901 and Ar 902 each independently represents an aromatic ring.)

[0040] X 1 and X 2 each independently represents a hydroxyl group or a carboxyl group.)

[0041] Z 1 represents a single bond or a group having a structure derived from styrene.)

[0042] h 1 and h 2 each independently represents an integer of 0 to 3.)

[0043] k 1 and k 2 each independently represents an integer of 0 to 3.)

[0044] h 1 and k 1 The sum of h 2 and k 2 is 3 or less.

[0045] n represents an integer of 1 or 2.

[0046] Among them, the structural unit represented by the formula (C1-1-1) and the structural unit represented by the formula (C1-1-2) each independently have at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.)

[0047] [4] The stripping agent composition or adhesive composition according to [2], wherein the novolak resin contains a structural unit represented by the following formula (C1-3-1) as the structural unit represented by the formula (C1-3).

[0048]

[0049] (In the formula (C1-3-1), R 801 represents a substituent substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group.

[0050] R 802 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0051] R 803 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group.

[0052] R 802 The group of R 803 and the group of R

[0053] Ar 801 represents a benzene ring, a naphthalene ring or a biphenyl structure.

[0054] X 11 represents a hydroxyl group or a carboxyl group.

[0055] Z 1 represents a single bond or a group having a structure derived from styrene.

[0056] h 11 each independently represents an integer from 0 to 4.

[0057] k 11 each independently represents an integer from 0 to 4.

[0058] Ar801 When it is a benzene ring, h 11 and k 11 have a total of 4 or less. When Ar 801 is a naphthalene ring, h 11 and k 11 have a total of 6 or less. When Ar 801 is a biphenyl structure, h 11 and k 11 have a total of 8 or less.

[0059] Among them, the structural unit represented by the formula (C1-3-1) has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0060] [5] The release agent composition or adhesive composition according to any one of [1] to [4], wherein the epoxy resin containing a siloxane skeleton contains a structure represented by the following formula (A).

[0061]

[0062] (In the formula (A), R 1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R 2 represents an alkylene group having 1 to 10 carbon atoms. Y represents a single bond or -O-. Ep represents a group represented by the following formula (A-1) or formula (A-2). * represents a bonding bond.)

[0063]

[0064] (In the formula (A-1) and formula (A-2), * represents a bonding bond.)

[0065] [6] The release agent composition or adhesive composition according to any one of [1] to [4], wherein the epoxy resin containing a siloxane skeleton is represented by any one of the following formulas (SE1) to (SE3).

[0066]

[0067] (In the formula (SE1), R 101 to R 110 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 101 represents a group represented by the following formula (EA). Y 101 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms (wherein, different from X 101 ). l represents 0 or an integer of 1 or more. m represents an integer of 1 or more. n represents 0 or an integer of 1 or more.)

[0068] In formula (SE2), R 201 ~R 207 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 201 and X 202 each independently represents a group represented by the following formula (EA). Y 201 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms. l represents an integer of 0 or more. m represents an integer of 0 or more.

[0069] In formula (SE3), R 301 ~R 304 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 301 ~X 304 each independently represents a group represented by the following formula (EA). m represents an integer of 1 to 3.)

[0070]

[0071] (In formula (EA), R 2 represents an alkylene group having 1 to 10 carbon atoms. Y represents a single bond or -O-. Ep represents a group represented by the following formula (A-1) or formula (A-2). * represents a bonding bond.)

[0072]

[0073] (In formula (A-1) and formula (A-2), * represents a bonding bond.)

[0074] [7] The stripping agent composition or the adhesive composition according to any one of [1] to [6], wherein the content of the epoxy resin having a siloxane skeleton is 5% by mass to 40% by mass relative to the novolak resin.

[0075] [8] A laminate, comprising: a semiconductor substrate or an electronic device layer, a light-transmissive support substrate, and a stripping agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate, wherein the stripping agent layer is a stripping agent layer formed from the stripping agent composition according to any one of [1] to [7].

[0076] [9] The laminate according to [8], wherein the laminate has an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0077]

[10] A method for manufacturing a processed semiconductor substrate or an electronic device layer, which includes: a 5A process of processing the semiconductor substrate of the laminate as described in [8]; or a 5B process of processing the electronic device layer of the laminate as described in [8]; and a 6A process of separating the semiconductor substrate processed by the 5A process from the support substrate; or a 6B process of separating the electronic device layer processed by the 5B process from the support substrate.

[0078]

[11] The method for manufacturing a processed semiconductor substrate or an electronic device layer according to

[10] , wherein the 6A process or the 6B process includes: a process of irradiating the laminate with a laser from the support substrate side.

[0079]

[12] A laminate, which has: a semiconductor substrate or an electronic device layer, a light-transmissive support substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, and the adhesive layer is an adhesive layer formed from the adhesive composition according to any one of [1] to [7].

[0080]

[13] A method for manufacturing a processed semiconductor substrate or an electronic device layer, which includes: a 5A process of processing the semiconductor substrate of the laminate as described in

[12] ; or a 5B process of processing the electronic device layer of the laminate as described in

[12] ; and a 6A process of separating the semiconductor substrate processed by the 5A process from the support substrate; or a 6B process of separating the electronic device layer processed by the 5B process from the support substrate.

[0081]

[14] The method for manufacturing a processed semiconductor substrate or an electronic device layer according to

[13] , wherein the 6A process or the 6B process includes: a process of irradiating the laminate with a laser from the support substrate side.

[0082] Advantages of the Invention

[0083] According to the present invention, it is possible to provide a release agent composition for photoirradiation peeling, a laminate using the release agent composition, and a method for manufacturing a processed semiconductor substrate or an electronic device layer. The release agent composition for photoirradiation peeling can form a release agent layer having excellent releasability and also excellent cleanability.

[0084] In addition, according to the present invention, it is possible to provide an adhesive composition for photoirradiation peeling, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or an electronic device layer. The adhesive composition for photoirradiation peeling can form an adhesive layer having excellent releasability and also excellent cleanability. Brief Description of the Drawings

[0085] Figure 1 FIG. is a schematic cross-sectional view of an example of the laminate in the first embodiment A.

[0086] Figure 2A FIG. is a schematic cross-sectional view (one) for explaining the manufacturing method of the laminate showing an example in the first embodiment A.

[0087] Figure 2B FIG. is a schematic cross-sectional view (two) for explaining the manufacturing method of the laminate showing an example in the first embodiment A.

[0088] Figure 2C FIG. is a schematic cross-sectional view (three) for explaining the manufacturing method of the laminate showing an example in the first embodiment A.

[0089] Figure 3 FIG. is a schematic cross-sectional view of an example of the laminate in the second embodiment A.

[0090] Figure 4 FIG. is a schematic cross-sectional view of another example of the laminate in the second embodiment A.

[0091] Figure 5A FIG. is a schematic cross-sectional view (one) for explaining the manufacturing method of the laminate showing an example in the second embodiment A.

[0092] Figure 5B FIG. is a schematic cross-sectional view (two) for explaining the manufacturing method of the laminate showing an example in the second embodiment A.

[0093] Figure 5C FIG. is a schematic cross-sectional view (three) for explaining the manufacturing method of the laminate showing an example in the second embodiment A.

[0094] Figure 5D FIG. is a schematic cross-sectional view (four) for explaining the manufacturing method of the laminate showing an example in the second embodiment A.

[0095] Figure 6A FIG. is a schematic cross-sectional view (one) for explaining the processing method of the laminate showing an example in the first embodiment A.

[0096] Figure 6B FIG. is a schematic cross-sectional view (two) for explaining the processing method of the laminate showing an example in the first embodiment A.

[0097] Figure 6CIt is a schematic cross-sectional view (Part 3) for explaining a method of processing a laminate representing an example in the first embodiment A.

[0098] Figure 6D It is a schematic cross-sectional view (Part 4) for explaining a method of processing a laminate representing an example in the first embodiment A.

[0099] Figure 7A It is a schematic cross-sectional view (Part 1) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0100] Figure 7B It is a schematic cross-sectional view (Part 2) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0101] Figure 7C It is a schematic cross-sectional view (Part 3) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0102] Figure 7D It is a schematic cross-sectional view (Part 4) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0103] Figure 7E It is a schematic cross-sectional view (Part 5) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0104] Figure 7F It is a schematic cross-sectional view (Part 6) for explaining a method of processing a laminate representing an example in the second embodiment A.

[0105] Figure 8 It is a schematic cross-sectional view of an example of a laminate in the first embodiment B.

[0106] Figure 9A It is a schematic cross-sectional view (Part 1) for explaining a method of manufacturing a laminate representing an example in the first embodiment B.

[0107] Figure 9B It is a schematic cross-sectional view (Part 2) for explaining a method of manufacturing a laminate representing an example in the first embodiment B.

[0108] Figure 10 It is a schematic cross-sectional view of an example of a laminate in the second embodiment B.

[0109] Figure 11A It is a schematic cross-sectional view (Part 1) for explaining a method of manufacturing a laminate representing an example in the second embodiment B.

[0110] Figure 11B It is a schematic cross-sectional view (Part II) for explaining a method of manufacturing a laminate representing an example in the second embodiment B.

[0111] Figure 11C It is a schematic cross-sectional view (Part III) for explaining a method of manufacturing a laminate representing an example in the second embodiment B.

[0112] Figure 12A It is a schematic cross-sectional view (Part I) for explaining a method of processing a laminate representing an example in the first embodiment B.

[0113] Figure 12B It is a schematic cross-sectional view (Part II) for explaining a method of processing a laminate representing an example in the first embodiment B.

[0114] Figure 12C It is a schematic cross-sectional view (Part III) for explaining a method of processing a laminate representing an example in the first embodiment B.

[0115] Figure 12D It is a schematic cross-sectional view (Part IV) for explaining a method of processing a laminate representing an example in the first embodiment B.

[0116] Figure 13A It is a schematic cross-sectional view (Part I) for explaining a method of processing a laminate representing an example in the second embodiment B.

[0117] Figure 13B It is a schematic cross-sectional view (Part II) for explaining a method of processing a laminate representing an example in the second embodiment B.

[0118] Figure 13C It is a schematic cross-sectional view (Part III) for explaining a method of processing a laminate representing an example in the second embodiment B.

[0119] Figure 13D It is a schematic cross-sectional view (Part IV) for explaining a method of processing a laminate representing an example in the second embodiment B.

[0120] Figure 13E It is a schematic cross-sectional view (Part V) for explaining a method of processing a laminate representing an example in the second embodiment B.

[0121] Figure 13F It is a schematic cross-sectional view (Part VI) for explaining a method of processing a laminate representing an example in the second embodiment B. Detailed implementation mode

[0122] (Release Agent Composition for Photoirradiation Release and Adhesive Composition for Photoirradiation Release)

[0123] The release agent composition for photoirradiation release of the present invention (hereinafter sometimes referred to as "release agent composition") contains: novolak resin, an epoxy resin having a siloxane skeleton, and a solvent.

[0124] The adhesive composition for photoirradiation release of the present invention (hereinafter sometimes referred to as "adhesive composition") contains: novolak resin, an epoxy resin having a siloxane skeleton, and a solvent.

[0125] Each component of the release agent composition and the adhesive composition will be described below.

[0126] <Novolak Resin>

[0127] The novolak resin has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0128] The novolak resin is, for example, a resin obtained by subjecting at least any one of phenolic compounds, carbazole compounds, and aromatic amine compounds to a condensation reaction with at least any one of aldehyde compounds, ketone compounds, and divinyl compounds and an arbitrary styrene compound under an acid catalyst.

[0129] Examples of the phenolic compound include: phenols, naphthols, anthrols, hydroxypyrenes, etc. Examples of the phenols include: phenol, cresol, xylenol, resorcinol, bisphenol A, p-tert-butylphenol, p-octylphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc. Examples of the naphthols include: 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis(6-hydroxynaphthyl)fluorene, etc. Examples of the anthrols include 9-anthrol, etc. Examples of the hydroxypyrenes include: 1-hydroxypyrene, 2-hydroxypyrene, etc.

[0130] As carbazole compounds, for example, the following can be cited: carbazole, 1,3,6,8 - tetranitrocarbazole, 3,6 - diamino - carbazole, 3,6 - dibromo - 9 - ethylcarbazole, 3,6 - dibromo - 9 - phenylcarbazole, 3,6 - dibromocarbazole, 3,6 - dichlorocarbazole, 3 - amino - 9 - ethylcarbazole, 3 - bromo - 9 - ethylcarbazole, 4,4'-bis(9H - carbazol - 9 - yl)biphenyl, 4 - glycidylcarbazole, 4 - hydroxycarbazole, 9 - (1H - benzotriazol - 1 - ylmethyl)-9H - carbazole, 9 - acetyl - 3,6 - diiodocarbazole, 9 - benzoylcarbazole, 9 - benzoylcarbazole - 6 - dialdehyde, 9 - benzylcarbazole - 3 - aldehyde, 9 - methylcarbazole, 9 - phenylcarbazole, 9 - vinylcarbazole, potassium carbazole, carbazole - N - formyl chloride, N - ethylcarbazole - 3 - aldehyde, N - ((9 - ethylcarbazol - 3 - yl)methylene)-2 - methyl - 1 - dihydroindoleamine, etc.

[0131] As aromatic amine compounds, for example, the following can be cited: diphenylamine, N - phenyl - 1 - naphthylamine, etc.

[0132] They can be used alone or in combination of two or more.

[0133] They can also have substituents. For example, they can have substituents on the aromatic ring.

[0134] As aldehyde compounds, for example, the following can be cited: saturated aliphatic aldehydes, unsaturated aliphatic aldehydes, heterocyclic aldehydes, aromatic aldehydes, etc. As saturated aliphatic aldehydes, for example, the following can be cited: formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, n - hexanal, 2 - methylbutyraldehyde, hexanal, undecanal, 7 - methoxy - 3,7 - dimethyloctanal, cyclohexanecarbaldehyde, 3 - methyl - 2 - butyraldehyde, 2 - ethylhexanal, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, etc. As unsaturated aliphatic aldehydes, for example, the following can be cited: acrolein, methacrolein, etc. As heterocyclic aldehydes, for example, the following can be cited: furfural, pyridinecarbaldehyde, etc. As aromatic aldehydes, for example, the following can be cited: benzaldehyde, naphthaldehyde, anthracenealdehyde, phenanthrenealdehyde, salicylaldehyde, phenylacetaldehyde, 3 - phenylpropionaldehyde, toluic aldehyde, (N,N - dimethylamino)benzaldehyde, acetoxybenzaldehyde, etc. Among them, saturated aliphatic aldehydes and aromatic aldehydes are preferred.

[0135] As ketone compounds, for example, diaryl ketone compounds can be cited. As diaryl ketone compounds, for example, the following can be cited: diphenyl ketone, phenylnaphthyl ketone, dinaphthyl ketone, phenyltolyl ketone, xylyl ketone, etc.

[0136] As divinyl compounds, for example, the following can be cited: divinylbenzene, dicyclopentadiene, tetrahydroindene, 4 - vinylcyclohexene, 5 - vinyl - 2 - norbornene, divinylpyrene, limonene, 5 - vinylnorbornadiene, etc.

[0137] They can be used individually or in combination of two or more.

[0138] As for the styrene compound, there is no particular limitation as long as it is a compound having a styrene structure. For example, styrene, α-methylstyrene, hydroxystyrene (vinylphenol), carboxystyrene (vinylbenzoic acid), alkylstyrene, tert-butoxystyrene, etc. can be cited.

[0139] They can be used individually or in combination of two or more.

[0140] The novolak resin is, for example, a novolak resin that deteriorates by absorbing light. The deterioration is, for example, photodecomposition.

[0141] The novolak resin contains, for example, at least any one of the structural units represented by the following formula (C1-1), the structural units represented by the following formula (C1-2), and the structural units represented by the following formula (C1-3).

[0142] For example, it is sufficient that there is at least one unit among the structural units represented by the following formula (C1-1), the structural units represented by the following formula (C1-2), and the structural units represented by the following formula (C1-3) contained in the novolak resin.

[0143]

[0144] In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom.

[0145] C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain; or represents a methylene group.

[0146] C 3 represents a group derived from an aliphatic polycyclic compound.

[0147] C 4 represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0148] C 5 represents a single bond or a group having a structure derived from styrene.

[0149] In formula (C1-1), at least any one of C 1 , C 2 and C 5 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0150] In formula (C1-2), at least any one of C 1 , C 3 and C 5 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0151] In formula (C1-3), at least any one of C 2 , C 4 and C 5 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0152] That is, the novolac resin contains, for example, one or more of the following structural units.

[0153] · A structural unit having the following bond (formula (C1-1)): a group derived from an aromatic compound containing a nitrogen atom and a group containing a tertiary carbon atom or a quaternary carbon atom having at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring in the side chain; or a bond between a methylene group and an arbitrary group having a structure derived from styrene.

[0154] · A structural unit having the following bond (formula (C1-2)): a bond between a group derived from an aromatic compound containing a nitrogen atom, a group derived from an aliphatic polycyclic compound, and an arbitrary group having a structure derived from styrene.

[0155] · A structural unit having the following bond (formula (C1-3)): a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol and a group containing a tertiary carbon atom or a quaternary carbon atom having at least one selected from the group consisting of a quaternary carbon atom and an aromatic ring in the side chain; or a bond between a methylene group and an arbitrary group having a structure derived from styrene.

[0156] The group derived from an aromatic compound containing a nitrogen atom of C 1 can be, for example, a group derived from carbazole, a group derived from N-phenyl-1-naphthylamine, a group derived from N-phenyl-2-naphthylamine, a group derived from N,N'-diphenyl-1,4-phenylenediamine, etc., but is not limited thereto.

[0157] The side chain of C 2 has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring, and contains a tertiary carbon atom or a quaternary carbon atom; or the methylene group can be, for example, a group derived from 1-naphthaldehyde, a group derived from 1-pyrenecarboxaldehyde, a group derived from 4-(trifluoromethyl)benzaldehyde, a group derived from 2-ethylhexanal, a group derived from acetaldehyde, etc., but is not limited thereto.

[0158] C 3 The group derived from an aliphatic polycyclic compound may be a group derived from dicyclopentadiene, but is not limited thereto.

[0159] C 4 is a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl, or a group derived from biphenol.

[0160] C 5 is a single bond or a group having a structure derived from styrene.

[0161] In the case where C 5 is a group having a structure derived from styrene, C 5 optionally has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0162] In a preferred embodiment, the novolak resin contains, for example, a structural unit represented by the following formula (C1-1-1) as the structural unit represented by the formula (C1-1).

[0163]

[0164] In the formula (C1-1-1), R 901 and R 902 represent substituents substituted on the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

[0165] R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

[0166] R 904 represents a hydrogen atom, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0167] R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0168] The group of R 904 and the group of R 905 optionally bond to each other to form a divalent group.

[0169] Examples of the substituents of the alkyl group and the alkenyl group include: a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, etc.

[0170] Examples of the substituents of the aryl group and the heteroaryl group include: a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, etc.

[0171] X 1 and X 2 each independently represents a hydroxyl group or a carboxyl group.

[0172] Z 1 represents a single bond or a group having a structure derived from styrene.

[0173] h 1 and h 2 each independently represents an integer from 0 to 3.

[0174] k 1 and k 2 each independently represents an integer from 0 to 3.

[0175] h 1 and k 1 The sum of h 2 and k 2 is 3 or less.

[0176] Among them, the structural unit represented by formula (C1-1-1) has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0177] For example, in formula (C1-1-1), when at least any one of R 904 , R 905 , and Z 1 has a hydroxyl group or a carboxyl group, k 1 and k 2 can also be 0.

[0178] For example, in formula (C1-1-1), when at least any one of R 904 and R 905 is an aryl group having a hydroxyl group or a carboxyl group, or Z 1 has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, k 1 and k 2 can also be 0.

[0179] For example, in formula (C1-1-1), when k 1 and k 2 are 0, it is preferable that at least any one of R 904 , R 905 , and Z 1 has a hydroxyl group or a carboxyl group.

[0180] For example, in formula (C1-1-1), when k 1 and k 2 are 0, it is preferable that at least any one of R 904and R 905 At least any one of them is an aryl group having a hydroxyl group or a carboxyl group, or Z 1 has at least any one group of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0181] In this specification, the number of carbon atoms of an optionally substituted alkyl group and an optionally substituted alkenyl group is usually 40 or less, preferably 30 or less, more preferably 20 or less from the viewpoint of solubility.

[0182] In this specification, the number of carbon atoms of an optionally substituted aryl group and a heteroaryl group is usually 40 or less, preferably 30 or less, more preferably 20 or less from the viewpoint of solubility.

[0183] In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0184] In this specification, examples of the substituent of the optionally substituted alkyl group include a halogen atom, an alkoxy group, a haloalkoxy group, etc.

[0185] In this specification, examples of the substituent of the optionally substituted alkenyl group include a halogen atom, an alkoxy group, a haloalkoxy group, etc.

[0186] In this specification, examples of the substituent of the optionally substituted aryl group include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, etc.

[0187] In this specification, examples of the substituent of the optionally substituted heteroaryl group include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, etc.

[0188] Specific examples of the optionally substituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, 2-ethylhexyl, etc., but are not limited thereto.

[0189] As specific examples of the optionally substituted alkenyl group, the following can be cited: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc., but not limited thereto.,

[0190] Specific examples of the optionally substituted aryl group include: phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-nitrophenyl, 4-cyanophenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 4-pentyloxyphenyl, 1-naphthyl, 2-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc., but not limited thereto.

[0191] Specific examples of the optionally substituted heteroaryl group include: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, etc., but not limited thereto.

[0192] As Z 1 , for example, the groups represented by the following formula (Z) can be cited.

[0193]

[0194] In formula (Z), R 910 represents a halogen atom, nitro group, cyano group, amino group, optionally substituted alkyl group, optionally substituted alkenyl group or optionally substituted aryl group.

[0195] R 911 represents a hydrogen atom or a methyl group.

[0196] X 10represents a hydroxyl group or a carboxyl group.

[0197] h 10 and k 10 each independently represents an integer from 0 to 3. h 10 and k 10 The sum of them is 5 or less.

[0198] * represents a bonding bond.

[0199] As specific examples of R 910 the specific examples listed in the description of R 901 and R 902 can be cited.

[0200] Hereinafter, specific examples of the structural unit represented by the formula (C1-1-1) are shown, but are not limited thereto. In addition, the substitution positions of the hydroxyl group and the carboxyl group on the aromatic ring are not limited either.

[0201]

[0202] In a preferred embodiment, the novolac resin contains, for example, a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1).

[0203]

[0204] In the formula (C1-1-2), Ar 901 and Ar 902 each independently represents an aromatic ring, R 901 ~R 905 、X 1 and X 2 、Z 1 、h 1 and h 2 and k 1 and k 2 represent the same meanings as described above.

[0205] h 1 and k 1 The sum of them is 3 or less. h 2 and k 2 The sum of them is 3 or less.

[0206] n represents an integer of 1 or 2.

[0207] Among them, the structural unit represented by the formula (C1-1-2) has at least any one of a hydroxyl group directly bonded to the aromatic ring and a carboxyl group directly bonded to the aromatic ring.

[0208] As the aromatic ring, for example, a benzene ring, a naphthalene ring, etc. can be cited.

[0209] For example, in formula (C1-1-2), when at least any one of R 904 , R 905 and Z 1 has a hydroxyl group or a carboxyl group, k 1 and k 2 can also be 0.

[0210] For example, in formula (C1-1-2), when at least any one of R 904 and R 905 is an aryl group having a hydroxyl group or a carboxyl group, or when Z 1 has at least any group of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, k 1 and k 2 can also be 0.

[0211] For example, in formula (C1-1-2), when k 1 and k 2 are 0, it is preferable that at least any one of R 904 , R 905 and Z 1 has a hydroxyl group or a carboxyl group.

[0212] For example, in formula (C1-1-2), when k 1 and k 2 are 0, it is preferable that at least any one of R 904 and R 905 is an aryl group having a hydroxyl group or a carboxyl group, or Z 1 has at least any group of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0213] Hereinafter, specific examples of the structural unit represented by formula (C1-1-2) are listed, but are not limited thereto. In addition, the substitution positions of the hydroxyl group and the carboxyl group on the aromatic ring are not limited.

[0214]

[0215] In a preferred embodiment, the novolac resin contains, for example, a structural unit represented by the following formula (C1-2-1) or (C1-2-2) as the structural unit represented by formula (C1-2).

[0216]

[0217] In the above formula, R 906 to R 909The substituents bonded to the ring each independently represent a halogen atom, nitro group, cyano group, amino group, hydroxyl group, carboxyl group, optionally substituted alkyl group, optionally substituted alkenyl group or optionally substituted aryl group. Specific examples and preferred numbers of carbon atoms of the halogen atom, optionally substituted alkyl group, optionally substituted alkenyl group and optionally substituted aryl group can be the same as those listed above, h 3 ~h 6 Each independently represents an integer from 0 to 3.

[0218] R 901 ~R 905 、X 1 and X 2 、Z 1 、h 1 and h 2 as well as k 1 and k 2 represent the same meanings as described above.

[0219] h 1 and k 1 The sum of h 2 and k 2 is 3 or less.

[0220] Among them, the structural unit represented by the formula (C1-2-1) and the structural unit represented by the formula (C1-2-2) each independently have at least any one of a hydroxyl group directly bonded to the aromatic ring and a carboxyl group directly bonded to the aromatic ring.

[0221] Hereinafter, specific examples of the structural units represented by the formulas (C1-2-1) and (C1-2-2) are listed, but are not limited thereto. In addition, the substitution positions of the hydroxyl group and carboxyl group on the aromatic ring are not limited either.

[0222]

[0223] In a preferred embodiment, the novolak resin contains, for example, a structural unit represented by the following formula (C1-3-1) as the structural unit represented by the formula (C1-3).

[0224]

[0225] In the formula (C1-3-1), R 801 represents a substituent substituted on the ring and each independently represents a halogen atom, nitro group, cyano group, amino group, optionally substituted alkyl group, optionally substituted alkenyl group or optionally substituted aryl group.

[0226] R 802 represents a hydrogen atom, optionally substituted aryl group or optionally substituted heteroaryl group.

[0227] R 803 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0228] R 802 groups of and R 803 groups of are optionally bonded to each other to form a divalent group.

[0229] Examples of the substituents for the aryl group and the heteroaryl group include: a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an alkyl group, an alkenyl group, etc.

[0230] Ar 801 represents a benzene ring, a naphthalene ring, or a biphenyl structure.

[0231] X 11 represents a hydroxyl group or a carboxyl group.

[0232] Z 1 represents a single bond or a group having a structure derived from styrene.

[0233] h 11 each independently represents an integer from 0 to 4.

[0234] k 11 each independently represents an integer from 0 to 4.

[0235] Ar 801 When Ar is a benzene ring, the sum of h 11 and k 11 is 4 or less. When Ar 801 is a naphthalene ring, the sum of h 11 and k 11 is 6 or less. When Ar 801 is a biphenyl structure, the sum of h 11 and k 11 is 8 or less.

[0236] Among them, the structural unit represented by the formula (C1-3-1) has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

[0237] For example, in the formula (C1-3-1), when at least any one of R 802 , R 803 and Z 1 has a hydroxyl group or a carboxyl group, k 11 can also be 0.

[0238] For example, in the formula (C1-3-1), when at least any one of R 802 and R 803 is an aryl group having a hydroxyl group or a carboxyl group, or Z 1In the case of having at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, k 11 may also be 0.

[0239] For example, in formula (C1-3-1), when k 11 is 0, at least any one of R 802 and R 803 is an aryl group having a hydroxyl group or a carboxyl group, or a heteroaryl group having a hydroxyl group or a carboxyl group.

[0240] Hereinafter, specific examples of the structural unit represented by formula (C1-3) are shown, but are not limited thereto.

[0241]

[0242] As described above, the novolak resin is, for example, a resin obtained by subjecting at least any one of phenolic compounds, carbazole compounds, and aromatic amine compounds to a condensation reaction with at least any one of aldehyde compounds, ketone compounds, and divinyl compounds and an arbitrary styrene compound in the presence of an acid catalyst.

[0243] In this condensation reaction, for example, relative to 1 equivalent of the benzene ring constituting the carbazole compound, an aldehyde compound or a ketone compound is usually used in a proportion of 0.1 to 10 equivalents.

[0244] When using a styrene compound to introduce at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring into the novolak resin, the styrene compound as a reaction raw material optionally has a protecting group. Examples of the styrene compound having a protecting group include tert-butoxystyrene.

[0245] In the above condensation reaction, an acid catalyst is usually used.

[0246] Examples of the acid catalyst include inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid, but are not limited thereto.

[0247] The amount of the acid catalyst is appropriately determined according to the type of the acid used, etc., and thus cannot be generally specified. It is usually appropriately determined within the range of 0.001 to 10,000 parts by mass relative to 100 parts by mass of the carbazole compound.

[0248] In the above condensation reaction, when any of the raw material compounds and the acid catalyst used is a liquid, sometimes the reaction can be carried out without using a solvent, but usually a solvent is used.

[0249] Such a solvent is not particularly limited as long as it does not hinder the reaction, and typically includes ether compounds, ether ester compounds, etc.

[0250] As the ether compound, for example, cyclic ether compounds such as tetrahydrofuran and dioxane can be cited.

[0251] As the ether ester compound, for example, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, etc. can be cited.

[0252] The reaction temperature is usually appropriately determined within the range of 40°C to 200°C. The reaction time varies depending on the reaction temperature, so it cannot be generally specified. Usually, it is appropriately determined within the range of 30 minutes to 50 hours.

[0253] After the reaction is completed, if necessary, purification and separation are carried out according to the conventional method, and the obtained novolak resin is used for the preparation of the stripping agent composition and the adhesive composition.

[0254] If one is a person skilled in the art, the manufacturing conditions of the novolak resin can be determined based on the above description and general technical knowledge without excessive burden. Therefore, the novolak resin can be manufactured.

[0255] The weight-average molecular weight of the novolak resin is usually 500 to 200,000. From the viewpoint of ensuring solubility in the solvent, etc., it is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, further preferably 5,000 or less, and even more preferably 3,000 or less. From the viewpoint of improving the strength of the film, etc., it is preferably 600 or more, more preferably 700 or more, still more preferably 800 or more, further preferably 900 or more, and even more preferably 1,000 or more.

[0256] It should be noted that in the present invention, the weight-average molecular weight, number-average molecular weight, and dispersity of the novolak resin can be measured, for example, using a GPC device (EcoSEC, HLC-8320GPC manufactured by TOSOH Corporation) and GPC columns (TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H manufactured by TOSOH Corporation), setting the column temperature to 40°C, using tetrahydrofuran as the eluent (dissolution solvent), setting the flow rate to 0.35 mL / minute, and using polystyrene (manufactured by Sigma Aldrich Corporation) as the standard sample.

[0257] The content of the novolak resin in the stripping agent composition is not particularly limited, and is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 99% by mass, and particularly preferably 70% by mass to 95% by mass with respect to the film constituent components of the stripping agent composition.

[0258] The content of the novolak resin in the adhesive composition is not particularly limited, and is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 99% by mass, and particularly preferably 70% by mass to 95% by mass with respect to the film constituent components of the adhesive composition.

[0259] It should be noted that in the present invention, the film constituent components refer to the components other than the solvent contained in the composition.

[0260] <Epoxy resin containing a siloxane skeleton>

[0261] The epoxy resin containing a siloxane skeleton has a siloxane bond and an epoxy group.

[0262] The epoxy resin containing a siloxane skeleton has, for example, two or more silicon atoms, and preferably four or more silicon atoms.

[0263] The epoxy resin containing a siloxane skeleton can be linear or cyclic.

[0264] The epoxy resin containing a siloxane skeleton preferably contains the structure represented by the following formula (A).

[0265]

[0266] (In formula (A), R 1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R 2 represents an alkylene group having 1 to 10 carbon atoms. Y represents a single bond or -O-. Ep represents a group represented by the following formula (A-1) or formula (A-2). * represents a bonding bond.)

[0267]

[0268] (In formula (A-1) and formula (A-2), * represents a bonding bond.)

[0269] As the "alkyl group" in the "substituted or unsubstituted alkyl group" of R 1 in formula (A), an alkyl group having 1 to 10 carbon atoms is preferred. Examples of the "alkyl group" include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, 2-cyclohexylmethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, etc.

[0270] As R in formula (A) 1 For the "alkenyl" in the "substituted or unsubstituted alkenyl", an alkenyl having 2 to 10 carbon atoms is preferred. Examples of the "alkenyl" include: vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, 2-cyclohexenyl, etc.

[0271] As R in formula (A) 1 The substituents of the alkyl in the "substituted or unsubstituted alkyl" and the substituents of the alkenyl in the "substituted or unsubstituted alkenyl" of R are not particularly limited. Examples include: halogen atom, cyano group, nitro group, alkyl-oxy group, alkyl-carbonyl group, alkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl-oxy group, alkenyl-carbonyl group, alkenyl-oxy-carbonyl group, alkenyl-carbonyl-oxy group, aryl group, aryl-oxy group, aryl-carbonyl group, aryl-oxy-carbonyl group, aryl-carbonyl-oxy group, etc.; or combinations thereof. The number of substituents is preferably 1 to 3, more preferably 1.

[0272] As R in formula (A) 1 For the "aryl" in the "substituted or unsubstituted aryl" of R, an aryl having 6 to 14 carbon atoms is preferred. Examples of the "aryl" include: phenyl, 1-naphthyl, 2-naphthyl, etc.

[0273] As R 1 The substituents of the aryl in the "substituted or unsubstituted aryl" of R are not particularly limited. Examples include: halogen atom, cyano group, nitro group, alkyl group, alkyl-oxy group, alkyl-carbonyl group, alkyl-oxy-carbonyl group, alkyl-carbonyl-oxy group, alkenyl group, alkenyl-oxy group, alkenyl-carbonyl group, alkenyl-oxy-carbonyl group, alkenyl-carbonyl-oxy group, aryl group, aryl-alkyl group, aryl-alkenyl group, aryl-oxy group, aryl-carbonyl group, aryl-oxy-carbonyl group, aryl-carbonyl-oxy group, etc.; or combinations thereof. The number of substituents is preferably 1 to 3, more preferably 1.

[0274] Examples of the "halogen atom" include: fluorine atom, chlorine atom, bromine atom, etc.

[0275] As R in formula (A) 1 is preferably substituted or unsubstituted alkyl, more preferably (unsubstituted) alkyl, still more preferably methyl, ethyl, propyl or isopropyl, and particularly preferably methyl.

[0276] Epoxy resins containing a siloxane skeleton are preferably represented by any one of the following formulas (SE1) to (SE3). It should be noted that in the epoxy resins containing a siloxane skeleton represented by the following formulas (SE1) to (SE3), the repeating units may be arranged randomly.

[0277]

[0278] (In formula (SE1), R 101 ~R 110 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 101 represents a group represented by the following formula (EA). Y 101 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms (wherein it is different from X 101 ). l represents an integer of 0 or 1 or more. m represents an integer of 1 or more. n represents an integer of 0 or 1 or more.

[0279] In formula (SE2), R 201 ~R 207 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 201 and X 202 each independently represents a group represented by the following formula (EA). Y 201 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms. l represents an integer of 0 or 1 or more. m represents an integer of 0 or 1 or more.

[0280] In formula (SE3), R 301 ~R 304 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. X 301 ~X 304 each independently represents a group represented by the following formula (EA). m represents an integer of 1 to 3.)

[0281]

[0282] (In formula (EA), R 2 represents an alkylene group having 1 to 10 carbon atoms. Y represents a single bond or -O-. Ep represents a group represented by the following formula (A - 1) or formula (A - 2). * represents a bonding bond.)

[0283]

[0284] (In formula (A - 1) and formula (A - 2), * represents a bonding bond.)

[0285] As R in formula (SE1)101 ~R 110 、 R in formula (SE2) 201 ~R 207 and R in formula (SE3) 301 ~R 304 Specific examples and preferred examples of substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted aryl groups, such as R in formula (A) 1 specific examples and preferred examples described in the description of

[0286] As Y in formula (SE1) 101 and Y 201 monovalent groups having 1 to 30 carbon atoms, such as any of the following (i) to (iv)

[0287] (i) Hydrocarbon groups having 7 to 30 carbon atoms.

[0288] (ii) Monovalent hydrocarbon groups having 2 to 30 carbon atoms formed by inserting at least one of an ether bond, a thioether bond, an amide bond, a carbamate bond, and an ester bond between carbon-carbon bonds of a hydrocarbon group.

[0289] (iii) Monovalent hydrocarbon groups having 1 to 30 carbon atoms in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom, a hydroxyl group, a nitro group, or a cyano group.

[0290] (iv) Monovalent hydrocarbon groups having 2 to 30 carbon atoms formed by inserting at least one of an ether bond, a thioether bond, an amide bond, a carbamate bond, and an ester bond between carbon-carbon bonds of a hydrocarbon group and in which at least one hydrogen atom in the hydrocarbon group is substituted with a halogen atom, a hydroxyl group, a nitro group, or a cyano group.

[0291] It should be noted that the carbon atoms in "monovalent groups having 1 to 30 carbon atoms" do not include the carbon atoms in cyano groups, amide bonds, carbamate bonds, and ester bonds.

[0292] Specific examples of the epoxy resin having a siloxane skeleton are as described below.

[0293] · Chain-like epoxy resins having a siloxane skeleton, such as 1,3,5-tris(2-(3,4-epoxycyclohexyl)ethyl)-1,1,3,5,5-pentamethyltrisiloxane.

[0294] · 2,4,6,8 - Tetrakis(4-(3,4-epoxycyclopentyl)butyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetrakis(3-(3,4-epoxycyclopentyl)propyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetrakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8,10-pentamethylcyclopentasiloxane and other epoxy resins containing a siloxane backbone.

[0295] The molecular weight of the epoxy resin containing a siloxane backbone is not particularly limited. The upper limit is preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, and particularly preferably 5,000 or less. The lower limit can be set, for example, at 200 or more, 400 or more, 600 or more, etc.

[0296] The epoxy equivalent of the epoxy resin containing a siloxane backbone is not particularly limited. The upper limit is preferably 1,000 g / eq. or less, more preferably 500 g / eq. or less, further preferably 300 g / eq. or less, and particularly preferably 250 g / eq. or less. The lower limit is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, further preferably 130 g / eq. or more, and particularly preferably 150 g / eq. or more.

[0297] The epoxy resin containing a siloxane backbone can be a commercially available product. As commercially available products, for example, there can be mentioned: "KF-105", "KF-1005", "KR-470" (main component: 2,4,6,8-tetrakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane) manufactured by Shin-Etsu Chemical Co., Ltd., "X-40-2667" (main component: 1,3,5-tris(2-(3,4-epoxycyclohexyl)ethyl)-1,1,3,5,5-pentamethyltrisiloxane), "EP-3400L" manufactured by ADEKA Corporation, etc.

[0298] The viscosity (25 °C) of the epoxy resin containing a siloxane backbone is not particularly limited, and is preferably 100 mPa·s to 10,000 mPa·s, more preferably 1,000 mPa·s to 5,000 mPa·s.

[0299] The content of the epoxy resin containing a siloxane backbone in the release agent composition is not particularly limited, and is preferably 1% by mass to 70% by mass, more preferably 3% by mass to 55% by mass, and particularly preferably 5% by mass to 40% by mass, relative to the novolac resin in the release agent composition.

[0300] The content of the epoxy resin having a siloxane skeleton in the adhesive composition is not particularly limited, and is preferably 1% by mass to 70% by mass, more preferably 3% by mass to 55% by mass, and particularly preferably 5% by mass to 40% by mass with respect to the novolak resin in the adhesive composition.

[0301] <Curing catalyst>

[0302] For the purpose of promoting the curing reaction and the like, the release agent composition may also contain a curing catalyst.

[0303] For the purpose of promoting the curing reaction and the like, the adhesive composition may also contain a curing catalyst.

[0304] There is no particular limitation on the curing catalyst, and examples thereof include amines, imidazoles, organic phosphines, Lewis acids, etc.

[0305] Examples of the amines include tertiary amines. Examples of the tertiary amines include 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU), triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc.

[0306] Examples of the imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, 2-heptadecylimidazole, 2-phenyl-1-benzyl-1H-imidazole, etc.

[0307] Examples of the organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc.

[0308] Examples of other curing catalysts include tetrasubstituted phosphonium tetrasubstituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate; tetraphenylborates such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate; and tetrabutylphosphonium O,O-diethyldithiophosphate, etc.

[0309] The amount of the curing catalyst contained in the release agent composition is not particularly limited, and is preferably 1% by mass to 20% by mass with respect to the epoxy resin having a siloxane skeleton in the release agent composition.

[0310] The amount of the curing catalyst contained in the adhesive composition is not particularly limited, and is preferably 1% by mass to 20% by mass with respect to the epoxy resin having a siloxane skeleton in the adhesive composition.

[0311] <Surfactant>

[0312] For the purpose of adjusting the liquid physical properties of the composition itself and the film physical properties of the resulting film, and preparing a release agent composition, an adhesive composition, etc. with high uniformity and good reproducibility, the release agent composition and the adhesive composition may also contain a surfactant.

[0313] Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate, etc. nonionic surfactants; fluorosurfactants such as EFTOP EF301, EF303, EF352 (manufactured by TOHKEMPRODUCTS Co., Ltd., trade name), MEGAFACE F171, F173, R-30, R-30N (manufactured by DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., trade name); silicone oxide polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0314] The surfactant may be used alone or in combination of two or more.

[0315] The amount of the surfactant in the release agent composition is usually 2% by mass or less relative to the film constituent components of the release agent composition.

[0316] The amount of the surfactant in the adhesive composition is usually 2% by mass or less relative to the film constituent components of the adhesive composition.

[0317] <Solvent>

[0318] The release agent composition contains a solvent.

[0319] The adhesive composition contains a solvent.

[0320] As the solvent, for example, a highly polar solvent that can well dissolve the above-mentioned novolac resin, epoxy resin containing a siloxane skeleton, and other film-forming components can be used. As needed, for the purpose of adjusting viscosity, surface tension, etc., a low polar solvent can also be used. It should be noted that in the present invention, a low polar solvent refers to a solvent defined as having a relative dielectric constant less than 7 at a frequency of 100 kHz, and a highly polar solvent refers to a solvent defined as having a relative dielectric constant of 7 or more at a frequency of 100 kHz. The solvent can be used alone or in combination of two or more kinds.

[0321] In addition, as the highly polar solvent, for example, the following can be cited: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylisobutyramide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone; ketone solvents such as ethyl methyl ketone, isophorone, cyclohexanone; cyano solvents such as acetonitrile, 3-methoxypropionitrile; polyol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 2,3-butanediol; monohydric alcohol solvents other than aliphatic alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, benzyl alcohol, 2-phenoxyethanol, 2-benzyloxyethanol, 3-phenoxybenzyl alcohol, tetrahydrofurfuryl alcohol; sulfoxide solvents such as dimethyl sulfoxide, etc.

[0322] As the low polar solvent, for example, the following can be cited: chlorine solvents such as chloroform, chlorobenzene; aromatic hydrocarbon solvents such as alkylbenzenes such as toluene, xylene, tetrahydronaphthalene, cyclohexylbenzene, decylbenzene; aliphatic alcohol solvents such as 1-octanol, 1-nonanol, 1-decanol; ether solvents such as tetrahydrofuran, dioxane, anisole, 4-methoxytoluene, 3-phenoxytoluene, dibenzyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether; ester solvents such as methyl benzoate, ethyl benzoate, butyl benzoate, isopentyl benzoate, bis(2-ethylhexyl) phthalate, dibutyl maleate, dibutyl oxalate, hexyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.

[0323] The content of the solvent is appropriately determined in consideration of the viscosity of the desired composition, the coating method employed, the thickness of the film to be produced, etc., and is 99% by mass or less of the whole composition, preferably 70 to 99% by mass relative to the whole composition, more preferably 85 to 97% by mass relative to the whole composition. That is, in this case, the amount of the film-forming component is preferably 1 to 30% by mass relative to the whole composition, more preferably 3 to 15% by mass relative to the whole composition.

[0324] The viscosities and surface tensions of the release agent composition and the adhesive composition are appropriately adjusted by considering various factors such as the coating method to be used, the desired film thickness, etc., and changing the types of solvents used, their ratios; the concentration of the film components, etc.

[0325] In one aspect of the present invention, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., the release agent composition and the adhesive composition contain a glycol-based solvent. It should be noted that the "glycol-based solvent" mentioned here refers to the general term for glycols, glycol monoethers, glycol diethers, glycol monoesters, glycol diesters, and glycol ester ethers.

[0326] An example of a preferred glycol-based solvent is represented by formula (G).

[0327]

[0328] In formula (G), R G1 each independently represents a linear or branched alkylene group having 2 to 4 carbon atoms, and R G2 and R G3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkyl acyl group in which the alkyl part is a linear or branched alkyl group having 1 to 8 carbon atoms, and n g is an integer from 1 to 6.

[0329] Specific examples of the linear or branched alkylene group having 2 to 4 carbon atoms include: ethylene, trimethylene, 1-methylethylene, tetramethylene, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, etc., but are not limited thereto.

[0330] Among them, from the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, reproducibly obtaining a composition that provides a film with high uniformity, etc., a linear or branched alkylene group having 2 to 3 carbon atoms is preferred, and a linear or branched alkylene group having 3 carbon atoms is more preferred.

[0331] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc.

[0332] Among them, from the viewpoints of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition that provides a film with high uniformity with good reproducibility, etc., methyl and ethyl are preferred, and methyl is more preferred.

[0333] Specific examples of the linear or branched alkyl group having 1 to 8 carbon atoms in the alkyl acyl group where the alkyl part is a linear or branched alkyl group having 1 to 8 carbon atoms include the same groups as the above specific examples.

[0334] Among them, from the viewpoints of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition that provides a film with high uniformity with good reproducibility, etc., methylcarbonyl and ethylcarbonyl are preferred, and methylcarbonyl is more preferred.

[0335] From the viewpoints of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition that provides a film with high uniformity with good reproducibility, etc., n g is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and most preferably 1.

[0336] From the viewpoints of obtaining a composition with high uniformity with good reproducibility, obtaining a composition with high storage stability with good reproducibility, obtaining a composition that provides a film with high uniformity with good reproducibility, etc., in formula (G), it is preferred that G2 R G3 and at least one of G2 R G3One of them is a linear or branched alkyl group having 1 to 8 carbon atoms, and the other is a hydrogen atom or an alkyl acyl group in which the alkyl moiety is a linear or branched alkyl group having 1 to 8 carbon atoms.

[0337] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition for providing a film with high uniformity, etc., the content of the glycol-based solvent in the stripping agent composition is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, further preferably 90% by mass or more, and still further preferably 95% by mass or more, relative to the solvent contained in the stripping agent composition.

[0338] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition for providing a film with high uniformity, etc., in the stripping agent composition, the film constituent components are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0339] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition for providing a film with high uniformity, etc., the content of the glycol-based solvent in the adhesive composition is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, further preferably 90% by mass or more, and still further preferably 95% by mass or more, relative to the solvent contained in the adhesive composition.

[0340] From the viewpoints of reproducibly obtaining a composition with high uniformity, reproducibly obtaining a composition with high storage stability, and reproducibly obtaining a composition for providing a film with high uniformity, etc., in the adhesive composition, the film constituent components are uniformly dispersed or dissolved in the solvent, preferably dissolved.

[0341] In the present invention, for the purpose of removing foreign matters, during the production of the stripping agent composition and the adhesive composition or after mixing all the components, the solvents, solutions, etc. used can be filtered using a filter or the like.

[0342] (Laminate <Embodiment A>)

[0343] Embodiment A of the laminate of the present invention has: a semiconductor substrate or an electronic device layer, a support substrate, and a stripping agent layer for photoirradiation peeling.

[0344] Embodiment A of the laminate of the present invention preferably further has an adhesive layer, and has the following constitution: a semiconductor substrate or an electronic device layer, a support substrate, a stripping agent layer for photoirradiation peeling, and an adhesive layer.

[0345] It should be noted that when the release agent layer of the present invention is formed to have not only a release function of separating the semiconductor substrate or the electronic device layer from the support substrate by light irradiation, but also an adhesive function of bonding the semiconductor substrate or the electronic device layer to the support substrate (that is, when the release agent layer is formed using a release agent composition containing components that exhibit both functions), the laminate may be formed not by two layers of a release agent layer and an adhesive layer, but by a single layer of a release agent layer having adhesive properties.

[0346] The support substrate has light transmissivity.

[0347] A release agent layer for light irradiation peeling is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0348] Embodiment A of the laminate is used for: separating the semiconductor substrate or the electronic device layer from the support substrate after the release agent layer absorbs light irradiated from the support substrate side.

[0349] The release agent layer for light irradiation peeling is a layer formed from the release agent composition for light irradiation peeling of the present invention described above.

[0350] Embodiment A of the laminate of the present invention is used for temporary bonding for processing the semiconductor substrate or the electronic device layer, and can be suitably used for processing such as thinning of the semiconductor substrate or the electronic device layer.

[0351] During the processing such as thinning of the semiconductor substrate, the semiconductor substrate is supported by the support substrate. On the other hand, after the processing of the semiconductor substrate, light is irradiated on the release agent layer, and then, the support substrate and the semiconductor substrate are separated. Due to the novolak resin contained in the release agent composition for light irradiation peeling of the present invention, in the release agent layer formed from the release agent composition, the novolak resin absorbs light (such as laser) to deteriorate (such as separate or decompose) the release agent layer. As a result, after light is irradiated on the release agent layer, the semiconductor substrate and the support substrate become easily separable.

[0352] In addition, during the processing such as thinning of the electronic device layer, the electronic device layer is supported by the support substrate. On the other hand, after the processing of the electronic device layer, light is irradiated on the release agent layer, and then, the support substrate and the electronic device layer are separated.

[0353] Through the release agent layer of the present invention, after light is irradiated, the semiconductor substrate or the electronic device layer and the support substrate become easily separable. Moreover, after the semiconductor substrate or the electronic device layer is separated from the support substrate, residues of the release agent layer and the adhesive layer remaining on the semiconductor substrate, the electronic device layer, or the support substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate and the like.

[0354] The wavelength of the light used for stripping is preferably, for example, a wavelength in the range of 250 to 600 nm, more preferably a wavelength in the range of 250 to 370 nm. More suitable wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of the light required for stripping is an irradiation amount that causes appropriate deterioration of the novolak resin, such as decomposition.

[0355] The light used for stripping can be a laser or non-laser light emitted from a light source such as an ultraviolet lamp.

[0356] It is divided into the case where the laminate has a semiconductor substrate and the case where the laminate has an electronic device layer, and will be described in detail below.

[0357] In the following <First Embodiment A>, the case where the laminate has a semiconductor substrate will be described, and in the following <Second Embodiment A>, the case where the laminate has an electronic device layer will be described.

[0358] <First Embodiment A>

[0359] The laminate having a semiconductor substrate is used for processing the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate. After the processing of the semiconductor substrate, light is irradiated on the release agent layer, and then the semiconductor substrate is separated from the support substrate.

[0360] <<Semiconductor Substrate>>

[0361] As the main material constituting the entire semiconductor substrate, there is no particular limitation as long as it can be used for such purposes, and examples include silicon, silicon carbide, compound semiconductors, etc.

[0362] The shape of the semiconductor substrate is not particularly limited. For example, it is disk-shaped. It should be noted that the disk-shaped semiconductor substrate does not need to have a completely circular surface shape. For example, the outer periphery of the semiconductor substrate may have a linear portion called an orientation flat or a notch called a groove.

[0363] As the thickness of the disk-shaped semiconductor substrate, it can be appropriately determined according to the use purpose of the semiconductor substrate, etc., and there is no particular limitation. For example, it is 500 to 1000 μm.

[0364] As the diameter of the disk-shaped semiconductor substrate, it can be appropriately determined according to the use purpose of the semiconductor substrate, etc., and there is no particular limitation. For example, it is 100 to 1000 mm.

[0365] The semiconductor substrate may also have bumps. A bump refers to a protruding terminal.

[0366] In a laminate, when the semiconductor substrate has bumps, the semiconductor substrate has bumps on the side of the support substrate.

[0367] In the semiconductor substrate, bumps are usually formed on the surface where the circuit is formed. The circuit can be single-layer or multi-layer. There is no particular limitation on the shape of the circuit.

[0368] In the semiconductor substrate, the surface (back surface) opposite to the surface having bumps is the surface for processing.

[0369] There is no particular limitation on the material, size, shape, structure, and density of the bumps of the semiconductor substrate.

[0370] Examples of the bumps include: spherical bumps, printed bumps, stud bumps, plated bumps, etc.

[0371] Generally, the height, radius, and pitch of the bumps are appropriately determined according to the conditions of the bump height of about 1 to 200 μm, the bump radius of 1 to 200 μm, and the bump pitch of 1 to 500 μm.

[0372] Examples of the material of the bumps include: low melting point solder, high melting point solder, tin, indium, gold, silver, copper, etc. The bumps can be composed of only a single component or multiple components. More specifically, examples include alloy plating mainly composed of Sn such as SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, etc.

[0373] In addition, the bumps can also have a laminated structure including a metal layer composed of at least any of these components.

[0374] An example of the semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.

[0375] <<Support Substrate>>

[0376] As the support substrate, as long as it is transparent to the light irradiated on the release agent layer and can support the semiconductor substrate during the processing of the semiconductor substrate, there is no particular limitation. For example, a glass support substrate can be cited.

[0377] There is no particular limitation on the shape of the support substrate. For example, a disc shape can be cited.

[0378] As for the thickness of the disc-shaped support substrate, it can be appropriately determined according to the size of the semiconductor substrate, etc., and there is no particular limitation. For example, it is 500 to 1000 μm.

[0379] The diameter of the disk-shaped support substrate may be appropriately determined according to the size of the semiconductor substrate or the like, and is not particularly limited. For example, it is 100 to 1000 mm.

[0380] An example of the support substrate is a glass wafer having a diameter of 300 mm and a thickness of about 700 μm.

[0381] <<Release agent layer>>

[0382] The release agent layer is a layer formed from a release agent composition.

[0383] The release agent layer is provided between the semiconductor substrate and the support substrate.

[0384] The release agent layer may be in contact with the support substrate or may be in contact with the semiconductor substrate.

[0385] The release agent layer is formed using the above-described release agent composition for photoirradiation peeling of the present invention.

[0386] The release agent composition of the present invention can be suitably used for forming a release agent layer of a laminate having: a semiconductor substrate, a support substrate, and a release agent layer provided between the semiconductor substrate and the support substrate. The laminate is used for: peeling the semiconductor substrate from the support substrate after the release agent layer absorbs light irradiated from the support substrate side.

[0387] One of the characteristics of the release agent layer obtained from the release agent composition of the present invention is that after photoirradiation, the semiconductor substrate can be easily peeled from the support substrate.

[0388] When forming the release agent layer from the release agent composition, it is considered that the novolak resin reacts with the epoxy resin having a siloxane skeleton.

[0389] The thickness of the release agent layer is not particularly limited, and is usually 0.05 to 3 μm. From the viewpoint of maintaining the film strength, it is preferably 0.07 μm or more, more preferably 0.1 μm or more, still more preferably 0.2 μm or more. From the viewpoint of avoiding non-uniformity due to a thick film, it is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and further preferably 0.5 μm or less.

[0390] Regarding the method for forming the release agent layer from the release agent composition, it is described in detail in the description part of <<Manufacturing method of an example of a laminate in the first embodiment A>> described below.

[0391] <<Adhesive layer>>

[0392] The adhesive layer is provided between the support substrate and the semiconductor substrate.

[0393] The adhesive layer is in contact with, for example, a semiconductor substrate. The adhesive layer may also be in contact with, for example, a support substrate.

[0394] The adhesive layer is not particularly limited, and a layer formed from an adhesive composition is preferred.

[0395] <<Adhesive Composition>>

[0396] Examples of the adhesive composition (hereinafter sometimes referred to as "the adhesive composition used in the present invention") include, but are not limited to, silicone-based adhesives, acrylic resin-based adhesives, epoxy resin-based adhesives, polyamide-based adhesives, polystyrene-based adhesives, polyimide adhesives, phenolic resin-based adhesives, etc.

[0397] Among them, during the processing of a semiconductor substrate or the like, it exhibits appropriate adhesive ability, can be appropriately peeled off after processing, has excellent heat resistance, and can be appropriately removed by a cleaning agent composition. Therefore, as the adhesive composition, a silicone-based adhesive is preferred.

[0398] The adhesive composition here is generally not the adhesive composition for photoirradiation peeling of the present invention.

[0399] In a preferred embodiment, the adhesive composition contains a polyorganosiloxane.

[0400] In addition, in another preferred embodiment, the adhesive composition contains a component that cures by a hydrosilylation reaction.

[0401] For example, the adhesive composition used in the present invention contains a cured component (A) that becomes an adhesive component. The adhesive composition used in the present invention may also contain a cured component (A) that becomes an adhesive component and a component (B) that does not cause a curing reaction. Here, examples of the component (B) that does not cause a curing reaction include polyorganosiloxane. It should be noted that in the present invention, "does not cause a curing reaction" does not mean that no curing reaction occurs, but rather that the curing reaction of the cured component (A) does not occur.

[0402] In a preferred embodiment, the component (A) may be a component that cures by a hydrosilylation reaction, or a polyorganosiloxane component (A') that cures by a hydrosilylation reaction.

[0403] In another preferred embodiment, component (A) contains, for example, as an example of component (A’): a polyorganosiloxane (a1) having an alkenyl group with 2 to 40 carbon atoms bonded to a silicon atom, a polyorganosiloxane (a2) having an Si—H group, and a platinum group metal-based catalyst (A2). Among them, the alkenyl group with 2 to 40 carbon atoms is optionally substituted. Examples of the substituent include: a halogen atom, a nitro group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, an aryl group, a heteroaryl group, etc.

[0404] In another preferred embodiment, the polyorganosiloxane component (A’) cured by a hydrosilylation reaction contains a polysiloxane (A1) and a platinum group metal-based catalyst (A2), and the polysiloxane (A1) contains a siloxane unit (Q unit) represented by SiO2, R 1 R 2 R 3 SiO 1 / 2 a siloxane unit (M unit) represented by, R 4 R 5 SiO 2 / 2 a siloxane unit (D unit) represented by, and R 6 SiO 3 / 2 a siloxane unit (T unit) represented by, and the polysiloxane (A1) contains a polyorganosiloxane (a1’) and a polyorganosiloxane (a2’), and the polyorganosiloxane (a1’) contains a siloxane unit (Q’ unit) represented by SiO2, R 1 ’R 2 ’R 3 ’SiO 1 / 2 a siloxane unit (M’ unit) represented by, R 4 ’R 5 ’SiO 2 / 2 a siloxane unit (D’ unit) represented by, and R 6 ’SiO 3 / 2 a siloxane unit (T’ unit) represented by, and contains at least one selected from the group consisting of M’ units, D’ units, and T’ units, and the polyorganosiloxane (a2’) contains a siloxane unit (Q” unit) represented by SiO2, R 1 ”R 2 ”R 3 ”SiO 1 / 2 a siloxane unit (M” unit) represented by, R 4 ”R 5 ”SiO 2 / 2 a siloxane unit (D” unit) represented by, and R 6 ”SiO 3 / 2One or more units in the group consisting of the siloxane units (T” units) shown, and containing at least one selected from the group consisting of M” units, D” units, and T” units.

[0405] It should be noted that (a1’) is an example of (a1), and (a2’) is an example of (a2).

[0406] R 1 ~R 6 Are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0407] R 1 ’~R 6 ’ are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, and at least one of R 1 ’~R 6 ’ is an optionally substituted alkenyl group. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0408] R 1 ”~R 6 ” are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, and at least one of R 1 ”~R 6 ” is a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.

[0409] The alkyl group can be any of linear, branched, or cyclic, preferably a linear or branched alkyl group, and its carbon number is not particularly limited, usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0410] Specific examples of the optionally substituted linear or branched alkyl group include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc. The number of carbon atoms is usually 1 to 14, preferably 1 to 10, more preferably 1 to 6. Among them, methyl is particularly preferred.

[0411] Specific examples of the optionally substituted cyclic alkyl group include, but are not limited to: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl and other cycloalkyl groups; bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, bicyclodecyl and other bicyclic alkyl groups, etc. The number of carbon atoms is usually 3 to 14, preferably 4 to 10, more preferably 5 to 6.

[0412] The alkenyl group can be either linear or branched, and the number of carbon atoms is not particularly limited. It is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.

[0413] Specific examples of the optionally substituted linear or branched alkenyl group include, but are not limited to, vinyl, allyl, butenyl, pentenyl, etc. The number of carbon atoms is usually 2 to 14, preferably 2 to 10, more preferably 2 to 6. Among them, vinyl and 2-propenyl are particularly preferred.

[0414] Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, etc. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, more preferably 5 to 6.

[0415] As described above, the polysiloxane (A1) contains a polyorganosiloxane (a1') and a polyorganosiloxane (a2'). The alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atom (Si-H group) contained in the polyorganosiloxane (a2') are cured by a hydrosilylation reaction using a platinum group metal-based catalyst (A2) to form a crosslinked structure. As a result, a cured film is formed.

[0416] The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and contains at least one selected from the group consisting of M' units, D' units, and T' units. As the polyorganosiloxane (a1'), two or more polyorganosiloxanes satisfying such conditions can also be used in combination.

[0417] Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units, and T' units include, but are not limited to, (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit, and M' unit).

[0418] In addition, when the polyorganosiloxane contained in the polyorganosiloxane (a1') includes two or more, combinations of (Q' unit and M' unit) and (D' unit and M' unit), (T' unit and M' unit) and (D' unit and M' unit), (Q' unit, T' unit, and M' unit) and (T' unit and M' unit) are preferred, but are not limited to these.

[0419] The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q'' units, M'' units, D'' units, and T'' units, and contains at least one selected from the group consisting of M'' units, D'' units, and T'' units. As the polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions can also be used in combination.

[0420] As two or more preferred combinations selected from the group consisting of the Q” unit, M” unit, D” unit, and T” unit, examples include: (M” unit and D” unit), (Q” unit and M” unit), (Q” unit, T” unit, and M” unit), but are not limited thereto.

[0421] The polyorganosiloxane (a1’) is composed of siloxane units in which its silicon atoms are bonded to alkyl groups and / or alkenyl groups. R 1 ’ to R 6 ’ The proportion of alkenyl groups in all the substituents represented by is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%. The remaining R 1 ’ to R 6 ’ can be an alkyl group.

[0422] The polyorganosiloxane (a2’) is composed of siloxane units in which its silicon atoms are bonded to alkyl groups and / or hydrogen atoms. R 1 ” to R 6 ” The proportion of hydrogen atoms in all the substituents and substituting atoms represented by is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%. The remaining R 1 ” to R 6 ” can be an alkyl group.

[0423] When the component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atom constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.

[0424] The weight average molecular weight of polyorganosiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and each is usually 500 to 1,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 5000 to 50,000.

[0425] It should be noted that in the present invention, the weight average molecular weight, number average molecular weight, and dispersity of polyorganosiloxanes (excluding the above-mentioned organosiloxane polymers) can be measured, for example, using a GPC device (EcoSEC manufactured by TOSOH Corporation, HLC-8320GPC) and GPC columns (TSKgel SuperMultipore HZ-N and TSKgel SuperMultipore HZ-H manufactured by TOSOH Corporation), setting the column temperature to 40 °C, using tetrahydrofuran as the eluent (dissolution solvent), setting the flow rate (flow velocity) to 0.35 mL / minute, and using polystyrene (manufactured by Showa Denko K.K., Shodex) as the standard sample.

[0426] The viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are not particularly limited, and each is usually 10 to 1,000,000 (mPa·s). From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 50 to 10,000 (mPa·s). It should be noted that the viscosities of the polyorganosiloxane (a1) and the polyorganosiloxane (a2) are values measured using an E-type rotational viscometer at 25°C.

[0427] The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other by a hydrosilylation reaction to form a film. Therefore, its curing mechanism is different from, for example, the mechanism via a silanol group. Therefore, any siloxane does not need to contain a silanol group or a functional group such as an alkoxy group that forms a silanol group by hydrolysis.

[0428] In a preferred embodiment of the present invention, the adhesive composition contains a polyorganosiloxane component (A') and a platinum group metal-based catalyst (A2).

[0429] Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si-H group of the polyorganosiloxane (a2).

[0430] Specific examples of the platinum-based metal catalyst include, but are not limited to, platinum black, platinum tetrachloride, chloroplatinic acid, the reaction product of chloroplatinic acid and a monohydric alcohol, the complex of chloroplatinic acid and an olefin, platinum diacetylacetonate, and other platinum-based catalysts.

[0431] Examples of the complex of platinum and an olefin include, but are not limited to, the complex of divinyltetramethyldisiloxane and platinum.

[0432] The amount of the platinum group metal-based catalyst (A2) is not particularly limited. Usually, it is in the range of 1.0 to 50.0 ppm relative to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2).

[0433] For the purpose of suppressing the progress of the hydrosilylation reaction, the polyorganosiloxane component (A') may also contain a polymerization inhibitor (A3).

[0434] The polymerization inhibitor is not particularly limited as long as it can suppress the progress of the hydrosilylation reaction. Specific examples thereof include alkynyl alcohols such as 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propyn-1-ol.

[0435] The amount of the polymerization inhibitor is not particularly limited, and is generally 1000.0 ppm or more and 10000.0 ppm or less from the viewpoint of obtaining its effect with respect to the total amount of the polyorganosiloxane (a1) and the polyorganosiloxane (a2), considering the prevention of excessive inhibition of the hydrosilylation reaction.

[0436] An example of the adhesive composition used in the present invention may contain both the cured component (A) and the component (B) that does not cause a curing reaction and serves as a release agent component, or may not contain it. By including such a component (B) in the adhesive composition, the obtained adhesive layer can be appropriately released with good reproducibility.

[0437] As such a component (B), typically, uncured polyorganosiloxanes can be cited. Specific examples thereof include: epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, etc., but are not limited thereto.

[0438] In addition, as the component (B), polydimethylsiloxane can be cited. The polydimethylsiloxane is optionally modified. Examples of the optionally modified polydimethylsiloxane include: epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, phenyl group-containing polydimethylsiloxane, etc., but are not limited thereto.

[0439] Preferred examples of the polyorganosiloxane as the component (B) include: epoxy group-containing polyorganosiloxanes, methyl group-containing polyorganosiloxanes, phenyl group-containing polyorganosiloxanes, etc., but are not limited thereto.

[0440] Although the weight average molecular weight of the polyorganosiloxane as the component (B) is not particularly limited, it is generally 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. In addition, although its dispersity is not particularly limited, it is generally 1.0 to 10.0. From the viewpoints of achieving appropriate release with good reproducibility, etc., it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight average molecular weight and dispersity can be measured by the above methods related to polyorganosiloxanes.

[0441] The viscosity of the polyorganosiloxane as the component (B) is not particularly limited, and is generally 1000 to 2,000,000 mm 2 / s. It should be noted that the viscosity value of the polyorganosiloxane as the component (B) is represented by kinematic viscosity and is centistokes (cSt) = mm 2 / s. It can also be obtained by dividing the viscosity (mPa·s) by the density (g / cm 3) is obtained. That is, its value can be obtained based on the viscosity and density measured at 25°C using an E-type rotational viscometer, and can be calculated according to the formula: kinematic viscosity (mm 2 / s) = viscosity (mPa·s) / density (g / cm 3 ).

[0442] Examples of the epoxy group-containing polyorganosiloxane include polyorganosiloxanes containing siloxane units (D 11 R 12 SiO 2 / 2 as shown (D 10 unit).

[0443] R 11 is a group bonded to a silicon atom and represents an alkyl group, and R 12 is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group. Specific examples of the alkyl group include the above examples.

[0444] The epoxy group in the organic group containing an epoxy group can be an independent epoxy group not condensed with other rings, or can be an epoxy group forming a condensed ring with other rings, such as 1,2-epoxycyclohexyl.

[0445] Specific examples of the organic group containing an epoxy group include 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited thereto.

[0446] In the present invention, as a preferred example of the epoxy group-containing polyorganosiloxane, epoxy group-containing polydimethylsiloxane can be cited, but is not limited thereto.

[0447] The epoxy group-containing polyorganosiloxane contains the above siloxane units (D 10 unit), but in addition to containing D 10 unit, it can also contain Q unit, M unit and / or T unit.

[0448] In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include: polyorganosiloxane composed only of D 10 unit; polyorganosiloxane containing D 10 unit and Q unit; polyorganosiloxane containing D 10 unit and M unit; polyorganosiloxane containing D 10 unit and T unit; polyorganosiloxane containing D 10 unit, Q unit and M unit; polyorganosiloxane containing D 10 unit, M unit and T unit; polyorganosiloxane containing D 10Polysiloxanes such as unit, Q unit, M unit, and T unit.

[0449] The epoxy group-containing polysiloxane is preferably a polydimethylsiloxane containing an epoxy group with an epoxy value of 0.1 to 5. In addition, although its weight average molecular weight is not particularly limited, it is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.

[0450] Specific examples of the epoxy group-containing polysiloxane include, but are not limited to, polysiloxanes represented by formulas (E1) to (E3).

[0451]

[0452] (m1 and n1 represent the number of each repeating unit and are positive integers.)

[0453]

[0454] (m2 and n2 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0455]

[0456] (m3, n3, and o3 represent the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

[0457] As the methyl group-containing polysiloxane, for example, those containing the siloxane unit (D 210 R 220 SiO 2 / 2 shown are mentioned, and preferably those containing the siloxane unit (D 200 unit) of polysiloxane. 21 R 21 SiO 2 / 2 shown are mentioned. 20 unit) of polysiloxane.

[0458] R 210 and R 220 are groups bonded to the silicon atom and each independently represents an alkyl group, and at least one is a methyl group. Specific examples of the alkyl group include the above examples.

[0459] R 21 is a group bonded to the silicon atom and represents an alkyl group. Specific examples of the alkyl group include the above examples. Among them, as R 21 , methyl is preferred.

[0460] In the present invention, as a preferred example of the methyl-containing polyorganosiloxane, polydimethylsiloxane can be cited, but it is not limited thereto.

[0461] The methyl-containing polyorganosiloxane contains the above-mentioned siloxane units (D 200 units or D 20 units), but in addition to containing D 200 units and D 20 units, it may also contain Q units, M units, and / or T units.

[0462] In a certain embodiment of the present invention, as specific examples of the methyl-containing polyorganosiloxane, there can be cited: a polyorganosiloxane composed only of D 200 units; a polyorganosiloxane containing D 200 units and Q units; a polyorganosiloxane containing D 200 units and M units; a polyorganosiloxane containing D 200 units and T units; a polyorganosiloxane containing D 200 units, Q units, and M units; a polyorganosiloxane containing D 200 units, M units, and T units; a polyorganosiloxane containing D 200 units, Q units, M units, and T units.

[0463] In a preferred embodiment of the present invention, as specific examples of the methyl-containing polyorganosiloxane, there can be cited: a polyorganosiloxane composed only of D 20 units; a polyorganosiloxane containing D 20 units and Q units; a polyorganosiloxane containing D 20 units and M units; a polyorganosiloxane containing D 20 units and T units; a polyorganosiloxane containing D 20 units, Q units, and M units; a polyorganosiloxane containing D 20 units, M units, and T units; a polyorganosiloxane containing D 20 units, Q units, M units, and T units.

[0464] As a specific example of the methyl-containing polyorganosiloxane, there can be cited the polyorganosiloxane represented by the formula (M1), but it is not limited thereto.

[0465]

[0466] (n4 represents the number of repeating units and is a positive integer.)

[0467] As the phenyl-containing polyorganosiloxane, for example, there can be cited those containing R 31 R 32 SiO2 / 2 The polysiloxane of the siloxane unit (D 30 unit) shown

[0468] R 31 is a group bonded to a silicon atom, representing a phenyl group or an alkyl group. R 32 is a group bonded to a silicon atom, representing a phenyl group. As a specific example of the alkyl group, the above examples can be cited, and methyl is preferred.

[0469] The phenyl group-containing polysiloxane contains the above siloxane unit (D 30 unit), but in addition to containing D 30 unit, it may also contain Q unit, M unit and / or T unit.

[0470] In a preferred embodiment of the present invention, as specific examples of the phenyl group-containing polysiloxane, there may be cited: a polysiloxane composed only of D 30 unit; a polysiloxane containing D 30 unit and Q unit; a polysiloxane containing D 30 unit and M unit; a polysiloxane containing D 30 unit and T unit; a polysiloxane containing D 30 unit, Q unit and M unit; a polysiloxane containing D 30 unit, M unit and T unit; a polysiloxane containing D 30 unit, Q unit, M unit and T unit.

[0471] As specific examples of the phenyl group-containing polysiloxane, there may be cited the polysiloxane represented by the formula (P1) or (P2), but it is not limited thereto.

[0472]

[0473] (m5 and n5 represent the number of each repeating unit and are positive integers.)

[0474]

[0475] (m6 and n6 represent the number of each repeating unit and are positive integers.)

[0476] The polysiloxane as the release agent component (B) can be a commercially available product or a synthesized polysiloxane.

[0477] Examples of commercially available polyorganosiloxanes include: WACKERSILICONE FLUID AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000) manufactured by Wacker Chemie AG, GENIOPLAST GUM, dimethyl silicone oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) manufactured by Shin-Etsu Chemical Co., Ltd., cyclic dimethyl silicone oil (KF-995); epoxy group-containing polyorganosiloxanes (trade names CMS-227, ECMS-327) manufactured by Gelest, epoxy group-containing polyorganosiloxanes (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd., epoxy group-containing polyorganosiloxane (BY16-839) manufactured by Dow Corning; phenyl group-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd., phenyl group-containing polyorganosiloxanes (TSF431, TSF433) manufactured by Momentive, etc., but are not limited thereto.

[0478] In one aspect, the adhesive composition used in the present invention contains both the cured component (A) and the component (B) that does not cause a curing reaction. In another aspect, it contains a polyorganosiloxane as the component (B).

[0479] An example of the adhesive composition used in the present invention may contain the component (A) and the component (B) at an arbitrary ratio. Considering the balance between adhesiveness and peelability, the ratio of the component (A) to the component (B) by mass ratio [(A):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0480] That is, in the case of containing a polyorganosiloxane component (A') cured by a hydrosilylation reaction, the ratio of the component (A') to the component (B) by mass ratio [(A'):(B)] is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

[0481] The viscosity of the adhesive composition used in the present invention is not particularly limited and is usually 500 to 20000 mPa·s at 25°C, preferably 1000 to 10000 mPa·s.

[0482] An example of the adhesive composition used in the present invention can be manufactured by mixing component (A) with component (B) used and a solvent.

[0483] The mixing order is not particularly limited. As an example of a method for easily and reproducibly manufacturing the adhesive composition, for example, a method of dissolving component (A) and component (B) in a solvent; a method of dissolving a part of component (A) and component (B) in a solvent, dissolving the remaining part in a solvent, and mixing the obtained solutions can be cited, but it is not limited thereto. It should be noted that when preparing the adhesive composition, it can also be appropriately heated within the range where the components do not decompose or deteriorate.

[0484] In the present invention, for the purpose of removing foreign matters, the solvent, solution, etc. used can also be filtered using a filter or the like during the production of the adhesive composition or after mixing all the components.

[0485] The thickness of the adhesive layer provided in the laminate of the present invention is not particularly limited, and is generally 5 to 500 μm. From the viewpoint of maintaining the film strength, it is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by a thick film, it is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 120 μm or less, and further preferably 70 μm or less.

[0486] The method for forming the adhesive layer from the adhesive composition is described in detail in the description part of <<Manufacturing method of an example of the laminate in the first embodiment A>> described below.

[0487] Hereinafter, an example of the configuration of the laminate of the first embodiment A will be described with reference to the drawings.

[0488] Figure 1 The laminate successively has: a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4.

[0489] The adhesive layer 2 and the release agent layer 3 are provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1. The release agent layer 3 is in contact with the adhesive layer 2 and the support substrate 4.

[0490] <<Manufacturing method of an example of the laminate in the first embodiment A>>

[0491] Taking the laminate shown in the laminate of the first embodiment A as an example, the manufacturing method of the laminate will be described below. Figure 1 Taking the laminate shown as an example, the manufacturing method of the laminate will be described below.

[0492] An example of the laminate of the present invention can be manufactured, for example, by a method including the following first process A to third process A.

[0493] First process A: A process of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer.

[0494] Second process A: A process of applying a release agent composition onto a support substrate to form a release agent layer.

[0495] Third process A: A process of heating the adhesive coating layer in a state where the adhesive coating layer is in contact with the release agent layer to form an adhesive layer.

[0496] The method of applying the adhesive composition is not particularly limited, and usually the spin coating method is used. It should be noted that a method of forming a coating film by spin coating or the like separately, forming a sheet-like coating film, and pasting the sheet-like coating film as the adhesive coating layer can be adopted.

[0497] The heating temperature of the applied adhesive composition varies depending on the type and amount of the adhesive component contained in the adhesive composition; whether a solvent is included; the boiling point of the solvent used; the desired thickness of the adhesive layer, etc., and thus cannot be generally specified. Usually, it is 80 to 150 °C, and the heating time is usually 30 seconds to 5 minutes.

[0498] When the adhesive composition contains a solvent, usually the applied adhesive composition is heated.

[0499] The film thickness of the adhesive coating layer obtained by applying the adhesive composition and, if necessary, heating it is usually about 5 to 500 μm, and is appropriately determined so as to finally fall within the range of the thickness of the above-mentioned adhesive layer.

[0500] The method of applying the release agent composition is not particularly limited, and usually the spin coating method is used.

[0501] The heating temperature of the applied release agent composition varies depending on the type and amount of the release agent component contained in the release agent composition; the desired thickness of the release agent layer, etc., and thus cannot be generally specified. From the viewpoint of reproducibly achieving an appropriate release agent layer, it is 80 °C or higher and 300 °C or lower. The heating time is appropriately determined usually within the range of 10 seconds to 10 minutes according to the heating temperature. The heating temperature is preferably 100 °C or higher and 280 °C or lower, more preferably 150 °C or higher and 250 °C or lower. The heating time is preferably 30 seconds or more and 8 minutes or less, more preferably 1 minute or more and 5 minutes or less.

[0502] Heating can be performed using a hot plate, an oven, etc.

[0503] The film thickness of the release agent obtained by heating the coating release agent composition, if necessary, is generally about 5 nm to 100 μm.

[0504] In the present invention, such coating layers can be joined together in contact with each other, while performing heat treatment or pressure reduction treatment or both, and applying a load in the thickness direction of the semiconductor substrate and the support substrate to bond the two layers, and then performing post-heat treatment, thereby obtaining the laminate of the present invention. It should be noted that any of the treatment conditions of heat treatment, pressure reduction treatment, or the combination of both is appropriately determined based on various situations such as the type of the adhesive composition, the specific composition of the release agent composition, the compatibility of the films obtained from the two compositions, the film thickness, and the obtained bonding strength.

[0505] From the viewpoint of removing the solvent from the composition and softening the adhesive coating layer to achieve proper adhesion to the release agent layer, etc., the heat treatment is generally appropriately determined within the range of 20 to 150 °C. In particular, from the viewpoint of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component (A), it is preferably 130 °C or lower, more preferably 90 °C or lower. The heating time is appropriately determined according to the heating temperature and the type of the adhesive. From the viewpoint of reliably achieving proper adhesion, it is generally 30 seconds or more, preferably 1 minute or more. From the viewpoint of suppressing the deterioration of the adhesive layer and other components, it is generally 10 minutes or less, preferably 5 minutes or less.

[0506] The pressure reduction treatment only needs to expose the mutually contacting adhesive coating layer and release agent layer to an air pressure of 10 to 10,000 Pa. The time of the pressure reduction treatment is generally 1 to 30 minutes.

[0507] From the viewpoint of obtaining a laminate with good separation of the substrate with good reproducibility, the two mutually contacting layers are preferably bonded by pressure reduction treatment, and more preferably by combining heat treatment and pressure reduction treatment.

[0508] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not cause adverse effects on the semiconductor substrate, the support substrate, and the two layers therebetween, and can firmly bond them, and is generally within the range of 10 to 1000 N.

[0509] From the viewpoint of achieving a sufficient curing speed, etc., the temperature of the post-heat treatment is preferably 120 °C or higher, and from the viewpoint of preventing the deterioration of the substrate and each layer, etc., the temperature of the post-heat treatment is preferably 260 °C or lower.

[0510] From the viewpoint of achieving appropriate bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.

[0511] Heating can be performed using a hot plate, an oven, etc. In the case of performing post-heating using a hot plate, either the semiconductor substrate or the support substrate of the laminate can be placed downward for heating. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferable to perform post-heating with the semiconductor substrate placed downward.

[0512] It should be noted that one of the purposes of the post-heating treatment is to achieve the adhesive layer and the release agent layer as more appropriate self-supporting films, and in particular, to appropriately achieve curing based on the hydrosilylation reaction.

[0513] The following uses Figures 2A - 2C to manufacture Figure 1 an example of a method for manufacturing a laminate will be described.

[0514] Figures 2A - 2C is a diagram for explaining one scheme for manufacturing a laminate.

[0515] First, a laminate ([[]] Figure 2A ) having an adhesive coating layer 2a formed on a semiconductor substrate 1 is prepared. This laminate can be obtained, for example, by coating an adhesive composition on the semiconductor substrate 1 and heating it.

[0516] In addition, a laminate ([[]] Figure 2B ) having a release agent layer 3 formed on a support substrate 4 is separately prepared. This laminate can be obtained, for example, by coating a release agent composition on the support substrate 4 and heating it.

[0517] Next, the laminate shown in [[[]] Figure 2A and the laminate shown in [[[]] Figure 2B are bonded together such that the adhesive coating layer 2a is in contact with the release agent layer 3. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; a hot plate) is disposed on the side of the semiconductor substrate 1 opposite to the surface in contact with the adhesive coating layer 2a, and the adhesive coating layer 2a is heated by the heating device to be cured and transformed into an adhesive layer 2 ([[]] Figure 2C ).

[0518] Through the process shown in [[[]] Figures 2A - 2C , a laminate can be obtained.

[0519] It should be noted that in [[[]] Figure 1In this case, the laminate sequentially laminates a semiconductor substrate 1, an adhesive layer 2, a release agent layer 3, and a support substrate 4. Therefore, it is listed by taking the above manufacturing method as an example. However, for example, in the case of manufacturing a laminate that sequentially laminates a semiconductor substrate 1, a release agent layer 3, an adhesive layer 2, and a support substrate 4, it can be manufactured by the following method, which includes: a first step A of coating a release agent composition on the surface of the semiconductor substrate and heating it if necessary to form a release agent layer; a second step A of coating an adhesive composition on the surface of the support substrate and heating it if necessary to form an adhesive coating layer; and a third step A of applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing at least one of a heat treatment and a pressure reduction treatment on the release agent layer of the semiconductor substrate and the adhesive coating layer of the support substrate to make them adhere, and then performing a post-heat treatment, thereby manufacturing the laminate.

[0520] It should be noted that as long as the effects of the present invention are not impaired, the coating and heating of each composition can be sequentially performed on any one of the substrates.

[0521] <<Second Embodiment A>>

[0522] The laminate having an electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer adheres to the support substrate. After the processing of the electronic device layer, light is irradiated on the release agent layer, and then the electronic device layer is separated from the support substrate.

[0523] <<Electronic Device Layer>>

[0524] The electronic device layer refers to a layer having an electronic device. In the present invention, it refers to a layer in which a plurality of semiconductor chip substrates are embedded in a sealing resin, that is, a layer including a plurality of semiconductor chip substrates and a sealing resin disposed between the semiconductor chip substrates.

[0525] Here, the "electronic device" refers to a component that constitutes at least a part of an electronic component. The electronic device is not particularly limited and can be an electronic device in which various mechanical structures and circuits are formed on the surface of a semiconductor substrate. The electronic device is preferably a composite body of a member made of metal or semiconductor and a resin that seals or insulates the member. The electronic device can be an electronic device in which a rewiring layer and / or a semiconductor element or other elements described later are sealed or insulated with a sealing material or an insulating material, and has a single-layer or multi-layer structure.

[0526] <<Support Substrate>>

[0527] As the support substrate, the same support substrate as the support substrate described in the <<Support Substrate>> column of the above <<First Embodiment A>> can be exemplified.

[0528] <<Release Agent Layer>>

[0529] The release agent layer is formed using the release agent composition for photoirradiation release of the present invention described above.

[0530] The detailed description of the release agent layer is as described in the column of <<Release Agent Layer>> of the above <First Embodiment A>.

[0531] <<Adhesive Layer>>

[0532] The adhesive layer is formed using the adhesive composition described above.

[0533] The detailed description of the adhesive layer is as described in the column of <<Adhesive Layer>> of the above <First Embodiment A>.

[0534] An example of the structure of the laminate of Second Embodiment A will be described below with reference to the drawings.

[0535] Figure 3 A schematic cross-sectional view showing an example of the laminate of Second Embodiment A.

[0536] Figure 3 The laminate of has, in order: a support substrate 24, a release agent layer 23, an adhesive layer 22, and an electronic device layer 26.

[0537] The electronic device layer 26 has: a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21.

[0538] The adhesive layer 22 and the release agent layer 23 are provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26. The release agent layer 23 is in contact with the adhesive layer 22 and the support substrate 24.

[0539] In addition, another example of the structure of the laminate of Second Embodiment A is shown in Figure 4 .

[0540] In the case where the release agent layer of the present invention is a release agent layer having an adhesive property that combines a release function and an adhesive function, the laminate may be formed of not two layers of a release agent layer and an adhesive layer but one layer of a release agent layer having an adhesive property.

[0541] Figure 4 A schematic cross-sectional view showing another example of the laminate.

[0542] Figure 4 The laminate of has, in order: a support substrate 24, a release agent layer 27 having an adhesive property, and an electronic device layer 26.

[0543] A release agent layer 27 having an adhesive property is provided between the support substrate 24 and the electronic device layer 26. The release agent layer 27 having an adhesive property can be produced by mixing the constituent components of a release agent composition for forming a release agent and the constituent components of an adhesive composition for forming an adhesive layer.

[0544] <<Manufacturing method of an example of the laminate in the second embodiment A>>

[0545] Taking the laminate shown in the laminate in the second embodiment A as an example, the manufacturing method of the laminate will be described below. Figure 3 Taking the laminate shown as an example, the manufacturing method of the laminate will be described below.

[0546] The laminate of the present invention can be manufactured, for example, by a method including the following first process A to fifth process A.

[0547] First process A: A process of coating a release agent composition on the surface of the above support substrate to form a release agent coating layer (and further heating if necessary to form a release agent layer).

[0548] Second process A: A process of coating an adhesive composition on the surface of the above release agent coating layer or release agent layer to form an adhesive coating layer (and further heating if necessary to form an adhesive layer).

[0549] Third process A: A process of placing a semiconductor chip substrate on the adhesive coating layer or adhesive layer and bonding the semiconductor chip substrate to the adhesive coating layer or adhesive layer while performing at least any one of heat treatment and pressure reduction treatment.

[0550] Fourth process A: A process of curing the adhesive coating layer by post-heat treatment to form an adhesive layer.

[0551] Fifth process A: A process of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0552] If the third process A is described in more detail, for example, the process of the following (iA) in the embodiment A can be cited.

[0553] (iA) Place the semiconductor chip substrate on the adhesive coating layer or adhesive layer, while performing at least one of heat treatment and pressure reduction treatment, apply a load in the thickness direction of the semiconductor chip substrate and the support substrate to make them closely contact, and bond the semiconductor chip substrate to the adhesive coating layer or adhesive layer.

[0554] It should be noted that the fourth process A can be carried out after the third process A attaches the semiconductor chip substrate to the adhesive coating layer, or can also be carried out together with the third process A. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer is heated to cure it, thereby jointly carrying out the adhesion of the semiconductor chip substrate to the adhesive coating layer and the curing from the adhesive coating layer to the adhesive layer, and attaching the adhesive layer to the semiconductor chip substrate.

[0555] In addition, the fourth process A can be carried out before the third process A, or the semiconductor chip substrate can be placed on the adhesive layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive layer is attached to the semiconductor chip substrate.

[0556] The coating method, the release agent composition after coating, the heating temperature of the adhesive composition, the heating method, etc. are as described in the above <Manufacturing method of an example of the laminate in the first embodiment A> of the above <First embodiment A>.

[0557] Regarding the manufacturing method of the laminate of the second embodiment A, the sequence will be further described in detail below with reference to the drawings. In this manufacturing method, manufacture Figure 3 the laminate shown.

[0558] As Figure 5A shown, a release agent coating layer 23' formed of a release agent composition is formed on the support substrate 24. At this time, the release agent coating layer 23' can also be heated to form a release agent layer 23.

[0559] Next, as Figure 5B shown, an adhesive coating layer 22' formed of an adhesive composition is formed on the release agent coating layer 23' or the release agent layer 23. At this time, the adhesive coating layer 22' can also be heated to form an adhesive layer 22.

[0560] Next, as Figure 5C shown, the semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive coating layer 22', and while performing at least one of heat treatment and pressure reduction treatment, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to make it adhere, and the semiconductor chip substrate 21 is attached to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive coating layer 22' is post-heated to cure it to form an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0561] It should be noted that when the adhesive coating layer 22' is post-heat-treated, the release agent coating layer 23' can be post-heat-treated together to form the release agent layer 23.

[0562] Next, as Figure 5D shown, the semiconductor chip substrate 21 fixed to the adhesive layer 22 is sealed with a sealing resin 25. In Figure 5D , a plurality of semiconductor chip substrates 21 temporarily bonded to the support substrate 24 with the adhesive layer 22 interposed therebetween are sealed with the sealing resin 25. An electronic device layer 26 having the semiconductor chip substrate 21 and the sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. Thus, the electronic device layer 26 becomes a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0563] <<<Sealing process>>>

[0564] The semiconductor chip substrate 21 is sealed with a sealing material.

[0565] As the sealing material for sealing the semiconductor chip substrate 21, a member that can insulate or seal a member made of metal or semiconductor is used.

[0566] In the present invention, as the sealing material, for example, a resin composition (sealing resin) is used. As the type of the sealing resin, as long as it can seal and / or insulate metal or semiconductor, there is no particular limitation. For example, an epoxy resin or a silicone resin is preferably used.

[0567] The sealing material may contain other components such as fillers in addition to the resin component. As the filler, for example, spherical silica particles can be cited.

[0568] In the sealing process, for example, the sealing resin heated to 130 to 170 °C is supplied onto the adhesive layer 22 in a state of maintaining a high viscosity and covering the semiconductor chip substrate 21, and compression molding is performed, whereby a layer formed of the sealing resin 25 is formed on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170 °C. In addition, the pressure applied to the semiconductor chip substrate 21 is, for example, 50 to 500 N / cm 2 .

[0569] (Manufacturing method of processed semiconductor substrate or electronic device layer <Embodiment A>)

[0570] If Embodiment A of the laminate of the present invention is used, a manufacturing method of a processed semiconductor substrate or a manufacturing method of a processed electronic device layer can be provided.

[0571] The manufacturing method of the processed semiconductor substrate uses the laminate described in the column of the above <First Embodiment A> of the above (laminate). In addition, the manufacturing method of the processed electronic device layer uses the laminate described in the column of the above <Second Embodiment A> of the above (laminate).

[0572] The manufacturing method of the processed semiconductor substrate will be described in the following <Third Embodiment A>, and the manufacturing method of the processed electronic device layer will be described in the following <Fourth Embodiment A>.

[0573] <Third Embodiment A>

[0574] The manufacturing method of the processed semiconductor substrate of the present invention includes: the following 5A process A and the following 6A process A. The manufacturing method of the processed semiconductor substrate may further include the following 7A process A.

[0575] Here, the 5A process A is a process of processing the semiconductor substrate in the laminate described in the column of the above <First Embodiment A>.

[0576] In addition, the 6A process A is a process A of separating the semiconductor substrate processed by the 5A process A from the support substrate.

[0577] In addition, the 7A process A is a process of cleaning the processed semiconductor substrate after the 6A process A.

[0578] The processing performed on the semiconductor substrate in the 5A process A is, for example, processing on the side opposite to the circuit surface of the wafer, and examples include thinning of the wafer achieved by grinding the back surface of the wafer. Then, for example, the formation of through-silicon vias (TSVs) etc. is performed, and then the thinned wafer is peeled off from the support substrate to form a laminate of wafers for three-dimensional mounting. In addition, for example, the formation of back surface electrodes of the wafer is also performed before and after the three-dimensional mounting. Heat of about 250 to 350 °C is applied in a state of being bonded to the support substrate during the thinning of the wafer and the TSV process. The laminate of the present invention usually includes an adhesive layer and has heat resistance against the applied heat.

[0579] The processing performed on the semiconductor substrate in the 5A process A may also be a process of dicing (singulation) the semiconductor substrate.

[0580] It should be noted that the processing is not limited to the above processing, and for example, it also includes the mounting process of semiconductor components in the case of temporarily bonding to the support substrate in order to support the substrate for mounting semiconductor components.

[0581] In the 6A process A, methods for separating (peeling) the semiconductor substrate from the support substrate include, but are not limited to, mechanical peeling using a tool with a sharp part after light irradiation of the release agent layer, peeling by tearing between the support and the semiconductor wafer, etc.

[0582] By irradiating light on the release agent layer from the support substrate side, the release agent layer deteriorates (e.g., separation or decomposition of the release agent layer) as described above. Then, for example, by pulling up either substrate, the semiconductor substrate can be easily separated from the support substrate.

[0583] It is not necessary to irradiate the entire area of the release agent layer with light. Even if areas irradiated with light and areas not irradiated with light coexist, as long as the peeling ability of the release agent layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the support substrate by a slight external force such as pulling up the support substrate. The ratio and positional relationship between the area irradiated with light and the area not irradiated with light vary depending on the type of adhesive used, its specific composition, the thickness of the adhesive layer, the thickness of the release agent layer, the intensity of the irradiated light, etc. However, for those skilled in the art, appropriate conditions can be set without excessive experimentation. Due to such circumstances, in the manufacturing method of the processed semiconductor substrate according to the present invention, for example, when the support substrate of the laminate used has light transmissivity, the light irradiation time can be shortened during peeling by light irradiation from the support substrate side. As a result, not only can an improvement in throughput be expected, but also physical stress for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the support substrate only by light irradiation.

[0584] Generally, the irradiation amount of light for peeling is 50 - 3000 mJ / cm 2 . The irradiation time is appropriately determined according to the wavelength and irradiation amount.

[0585] The wavelength of the light for peeling is, as described above, preferably a wavelength of 250 - 600 nm, more preferably a wavelength of 250 - 370 nm. More appropriate wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for peeling is the irradiation amount that causes appropriate deterioration of the novolac resin, such as decomposition.

[0586] The light for peeling can be a laser or non - laser light emitted from a light source such as an ultraviolet lamp.

[0587] A cleaning agent composition can be sprayed on the surface of at least any one of the separated semiconductor substrate and the support substrate, or the separated semiconductor substrate or support substrate can be immersed in the cleaning agent composition to clean the substrate.

[0588] In addition, the surface of a processed semiconductor substrate or the like can be cleaned by removing a tape or the like.

[0589] As an example of cleaning the substrate, a 7A process A for cleaning the processed semiconductor substrate can be performed after the 6A process A.

[0590] The following substances can be cited as the cleaning agent composition for cleaning.

[0591] The cleaning agent composition generally contains a salt and a solvent.

[0592] As a preferred example of the cleaning agent composition, a cleaning agent composition containing a quaternary ammonium salt and a solvent can be cited.

[0593] The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it is used for such purposes.

[0594] As such a quaternary ammonium cation, typically a tetra(hydrocarbon)ammonium cation can be cited. On the other hand, as the anion paired with it, the following can be cited: hydroxide ion (OH － ); fluoride ion (F － ), chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ) and other halogen ions; tetrafluoroborate ion (BF4 － ); hexafluorophosphate ion (PF6 － ), etc., but not limited thereto.

[0595] The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.

[0596] In the quaternary ammonium salt, the halogen atom can be contained in the cation or in the anion, and is preferably contained in the anion.

[0597] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.

[0598] As specific examples of the hydrocarbon group in tetra(hydrocarbon)ammonium fluoride, the following can be cited: an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, etc.

[0599] In a more preferred embodiment, the tetra(hydrocarbon)ammonium fluoride contains tetraalkylammonium fluoride.

[0600] As specific examples of the tetraalkylammonium fluoride, the following can be cited: tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride), etc., but not limited thereto. Among them, tetrabutylammonium fluoride is preferred.

[0601] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride may also be used in the form of hydrates. In addition, tetra(hydrocarbon)ammonium fluoride and other quaternary ammonium salts may be used alone or in combination of two or more.

[0602] The amount of the quaternary ammonium salt is not particularly limited as long as it is dissolved in the solvent contained in the cleaning agent composition, and is usually 0.1 to 30% by mass relative to the cleaning agent composition.

[0603] The solvent contained in the cleaning agent composition is not particularly limited as long as it is used for this purpose and can dissolve salts such as quaternary ammonium salts. From the viewpoints of obtaining a cleaning agent composition with excellent cleaning performance with good reproducibility and dissolving salts such as quaternary ammonium salts well to obtain a cleaning agent composition with excellent uniformity, etc., the cleaning agent composition preferably contains one or more amide solvents.

[0604] As a preferred example of the amide solvent, an amide derivative represented by the formula (Z) can be cited.

[0605]

[0606] In the formula, R 0 represents ethyl, propyl or isopropyl, preferably ethyl, isopropyl, more preferably ethyl. R A and R B each independently represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms can be any of linear, branched and cyclic, and specifically, methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, etc. can be cited. Among them, as R A and R B , methyl or ethyl is preferred, and both being methyl or ethyl is more preferred, and both being methyl is even more preferred.

[0607] Examples of the amide derivative represented by the formula (Z) include N,N-dimethylpropanamide, N,N-diethylpropanamide, N-ethyl-N-methylpropanamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, N-ethyl-N-methylisobutyramide, etc. Among them, N,N-dimethylpropanamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropanamide is more preferred.

[0608] The amide derivative represented by the formula (Z) can be synthesized by the substitution reaction of the corresponding carboxylic acid ester and amine, or a commercially available product can be used.

[0609] As another example of the preferred amide solvent, a lactam compound represented by the formula (Y) can be cited.

[0610]

[0611] In formula (Y), R 101 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 102 represents an alkylene group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, etc. Specific examples of the alkylene group having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited thereto.

[0612] Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., and they can be used alone or in combination of two or more.

[0613] In a preferred embodiment, the lactam compound represented by formula (Y) includes 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam). In a more preferred embodiment, it includes N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP). In an even more preferred embodiment, it includes N-methylpyrrolidone (NMP).

[0614] The cleaning agent composition may also contain one or more other organic solvents different from the above amide compounds.

[0615] Such other organic solvents are not particularly limited as long as they are used for this purpose and are compatible with the above amide compounds.

[0616] Preferred other solvents include alkylene glycol dialkyl ethers, aromatic hydrocarbon compounds, cyclic structure-containing ether compounds, etc., but are not limited thereto.

[0617] Regarding the amount of other organic solvents different from the above amide compounds, as long as the quaternary ammonium salt contained in the cleaning agent composition does not precipitate or separate and is uniformly mixed with the above amide compounds, it is generally appropriately determined to be 95% by mass or less in the solvents contained in the cleaning agent composition.

[0618] It should be noted that the cleaning agent composition may also contain water as a solvent. However, from the viewpoints of avoiding corrosion of the substrate, etc., it is generally intended to use only organic solvents as solvents. It should be noted that in this case, the water of hydration of salts and the trace amounts of water contained in the organic solvents are included in the cleaning agent composition, and this is not all denied. The water content of the cleaning agent composition is usually 5% by mass or less.

[0619] Regarding the constituent elements and method elements related to the above-described processes of Embodiment A of the method for manufacturing a processed semiconductor substrate of the present invention, various modifications can be made as long as the gist of the present invention is not deviated from.

[0620] Embodiment A of the method for manufacturing a processed semiconductor substrate of the present invention may also include processes other than the above-described processes.

[0621] In the peeling method of the present invention, when the semiconductor substrate or the support substrate of the laminate of the present invention has light-transmitting properties, the semiconductor substrate of the laminate is separated from the support substrate by irradiating the release agent layer with light from the semiconductor substrate side or the support substrate side.

[0622] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and peelably through an adhesive layer and a release agent layer. Therefore, for example, when the support substrate has light-transmitting properties, the semiconductor substrate can be easily separated from the support substrate by irradiating the release agent layer with light from the support substrate side of the laminate. Usually, the peeling is performed after processing the semiconductor substrate of the laminate.

[0623] Use Figures 6A - 6D An example of the third Embodiment A will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0624] First, a laminate ( Figure 6A ) is prepared. This laminate is the same laminate as the laminate shown in Figure 1 and Figure 2C .

[0625] Next, the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2 is polished using a polishing device (not shown) to thin the semiconductor substrate 1 ( Figure 6B ). It should be noted that formation of a through electrode or the like may also be performed on the thinned semiconductor substrate 1.

[0626] Next, after irradiating the release agent layer 3 with light from the support substrate 4 side, a peeling device (not shown) is used to separate the thinned semiconductor substrate 1 from the support substrate 4 ( Figure 6C ).

[0627] In this way, a thinned semiconductor substrate 1 ( Figure 6D ) is obtained.

[0628] Here, residues of the adhesive layer 2 and the release agent layer 3 sometimes remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 using a cleaning agent composition to remove the residues of the adhesive layer 2 and the release agent layer 3 from the semiconductor substrate 1.

[0629] <Fourth Embodiment A>

[0630] The method for manufacturing a processed electronic device layer of the present invention includes: the following 5B process A and the following 6B process A. The method for manufacturing a processed electronic device layer may further include the following 7B process A.

[0631] Here, the 5B process A is a process of processing the electronic device layer in the laminate described in the column of <Second Embodiment A> above.

[0632] In addition, the 6B process A is a process of separating the electronic device layer processed by the 5B process A from the support substrate.

[0633] In addition, the 7B process A is a process of cleaning the processed electronic device layer after the 6B process A.

[0634] The following uses Figures 7A - 7F to illustrate a specific example of the Fourth Embodiment A.

[0635] Examples of the processing performed on the electronic device layer in the 5B process A include a grinding process, a wiring layer formation process, and the like.

[0636] <<Grinding Process>>

[0637] The grinding process is a process of grinding the resin portion of the layer of the sealing resin 25 in the electronic device layer 26 so that a part of the semiconductor chip substrate 21 is exposed.

[0638] The grinding of the sealing resin portion is, for example, as Figure 7B shown, by grinding the layer of the sealing resin 25 of the laminate shown to be approximately the same thickness as the semiconductor chip substrate 21. It should be noted that Figure 7A the laminate shown is the same laminate as the laminates shown in Figure 7A and Figure 3 and Figure 5D shown.

[0639] <<Wiring Layer Formation Process>>

[0640] The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above grinding process.

[0641] In Figure 7C , a wiring layer 28 is formed on the electronic device layer 26 including the semiconductor chip substrate 21 and the layer of the sealing resin 25.

[0642] The wiring layer 28, also known as the RDL (Redistribution Layer), is a wiring body of a thin film that constitutes the wiring connected to the substrate and can have a single-layer or multi-layer structure. The wiring layer 28 can be a layer formed by forming wiring between dielectrics (such as silicon oxide (SiO X ) and photosensitive resins such as photosensitive epoxy resins) using conductors (such as metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys), but is not limited thereto.

[0643] As a method for forming the wiring layer 28, for example, the following methods can be cited.

[0644] First, a dielectric layer such as silicon oxide (SiO X ) or a photosensitive resin is formed on the layer of the sealing resin 25. The dielectric layer made of silicon oxide can be formed, for example, by sputtering, vacuum evaporation, etc. The dielectric layer formed of the photosensitive resin can be formed, for example, by coating the photosensitive resin on the layer of the sealing resin 25 using methods such as spin coating, dipping, roller blade, spray coating, and slit coating.

[0645] Next, wiring is formed on the dielectric layer using a conductor such as metal. As a method for forming the wiring, for example, known semiconductor process methods such as photolithography (resist photolithography) and etching can be used. As such photolithography, for example, photolithography using a positive resist material and photolithography using a negative resist material can be cited.

[0646] In the method for manufacturing the laminate of the fourth embodiment A, bumps can be further formed or components can be mounted on the wiring layer 28. The mounting of components on the wiring layer 28 can be performed, for example, using a mounter or the like.

[0647] The laminate of the fourth embodiment A can be a laminate manufactured in the process based on the following technology: a fan-out technology in which the terminals provided on the semiconductor chip substrate are mounted on the wiring layer extending outside the chip region.

[0648] In the 6B process A, examples of the method for separating (peeling) the electronic device layer from the support substrate include mechanical peeling using a tool with a sharp part and peeling by tearing between the support and the electronic device layer after light irradiation of the peeling agent layer, but are not limited thereto.

[0649] By irradiating light on the peeling agent layer from the support substrate side, the deterioration of the peeling agent layer (such as separation or decomposition of the peeling agent layer) occurs as described above, and then, for example, by pulling up either substrate, the electronic device layer can be easily separated from the support substrate.

[0650] Figures 7D - 7E is a schematic cross-sectional view for explaining a method for separating a laminated body. Figure 7F This is a schematic cross-sectional view for explaining a method for cleaning a laminated body after separation. Figures 7D - 7F , which can illustrate an embodiment of a method for manufacturing a semiconductor package (electronic component).

[0651] like Figure 7D As shown, the step of separating the laminated body is a step of irradiating the release agent layer 23 with light (arrow) via the support substrate 24 to change the release agent layer 23 , thereby separating the electronic device layer 26 from the support substrate 24 .

[0652] After the release agent layer 23 is irradiated with light (arrow) to deteriorate the release agent layer 23, Figure 7E As shown, the support substrate 24 is separated from the electronic device layer 26 .

[0653] The conditions and method of irradiating the release agent layer 23 with light are as described in the above-mentioned section of <Third Embodiment A>.

[0654] The substrate may be cleaned by spraying the cleaning composition on the surface of at least any one of the separated electronic device layer and the supporting substrate, or by immersing the separated electronic device layer or the supporting substrate in the cleaning composition.

[0655] Alternatively, the surface of the processed electronic device layer or the like may be cleaned using a removal tape or the like.

[0656] For example, in Figure 7E In the process, after the separation step, the adhesive layer 22 and the release agent layer 23 are attached to the electronic device layer 26. By using a cleaning agent composition such as an acid or an alkali, the adhesive layer 22 and the release agent layer 23 are decomposed and removed. By removing the release agent layer and the adhesive layer, the following can be appropriately obtained: Figure 7F The processed electronic device layer (electronic component) is shown.

[0657] The constituent elements and method elements related to the above-mentioned steps of the method for producing a processed electronic device layer of the present invention may be variously modified without departing from the gist of the present invention.

[0658] Embodiment A of the method for producing a processed electronic device layer of the present invention may include steps other than the above-mentioned steps.

[0659] In Embodiment A of the laminate of the present invention, the electronic device layer and the support substrate are temporarily bonded appropriately and peelably via an adhesive layer. Therefore, for example, when the support substrate has light transmissivity, the electronic device layer can be easily separated from the support substrate by irradiating light from the support substrate side of the laminate onto the release agent layer. Usually, the peeling is performed after processing the electronic device layer of the laminate.

[0660] (Laminate <Embodiment B>)

[0661] Embodiment B of the laminate of the present invention includes: a semiconductor substrate or an electronic device layer, a support substrate, and an adhesive layer for light irradiation peeling.

[0662] The support substrate has light transmissivity.

[0663] The adhesive layer for light irradiation peeling is provided between the semiconductor substrate or the electronic device layer and the support substrate.

[0664] Embodiment B of the laminate is used for: the semiconductor substrate or the electronic device layer to be peeled from the support substrate after the adhesive layer absorbs the light irradiated from the support substrate side.

[0665] The adhesive layer for light irradiation peeling is a layer formed from the above-described adhesive composition for light irradiation peeling of the present invention.

[0666] In Embodiment B of the laminate, by using the adhesive layer formed from the adhesive composition for light irradiation peeling of the present invention, excellent peelability can be achieved even without a release agent layer.

[0667] Embodiment B of the laminate of the present invention is used for temporarily bonding in order to process the semiconductor substrate or the electronic device layer, and can be suitably used for processing such as thinning of the semiconductor substrate or the electronic device layer.

[0668] During processing such as thinning of the semiconductor substrate, the semiconductor substrate is supported by the support substrate. On the other hand, after processing the semiconductor substrate, the adhesive layer is irradiated with light, and then, the support substrate and the semiconductor substrate are separated. Due to the novolak resin contained in the adhesive composition for light irradiation peeling of the present invention, in the adhesive layer formed from the adhesive composition, the novolak resin absorbs light (such as laser) to deteriorate (such as separate or decompose) the adhesive layer. As a result, after irradiating the adhesive layer with light, the semiconductor substrate and the support substrate become easily peelable.

[0669] In addition, during processing such as thinning of the electronic device layer, the electronic device layer is supported by the support substrate. On the other hand, after processing the electronic device layer, the adhesive layer is irradiated with light, and then, the support substrate and the electronic device layer are separated.

[0670] Through the adhesive layer of the present invention, after light irradiation, the semiconductor substrate or the electronic device layer and the support substrate become easily separable. Moreover, after the semiconductor substrate or the electronic device layer is separated from the support substrate, residues of the adhesive layer remaining on the semiconductor substrate, the electronic device layer, or the support substrate can be removed, for example, by a cleaning agent composition for cleaning the semiconductor substrate or the like.

[0671] The adhesive layer of the laminate of the present invention is formed of a single layer, and thus can be easily manufactured with excellent productivity.

[0672] The wavelength of the light for separation is, for example, preferably a wavelength of 250 to 600 nm, more preferably a wavelength of 250 to 370 nm. More appropriate wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of the light required for separation is an irradiation amount that causes appropriate deterioration of the novolac resin, for example, decomposition.

[0673] The light for separation can be a laser or non-laser light emitted from a light source such as an ultraviolet lamp.

[0674] The cases where the laminate has a semiconductor substrate and the case where the laminate has an electronic device layer are separately described in detail below.

[0675] The case where the laminate has a semiconductor substrate is described in <First Embodiment B> below, and the case where the laminate has an electronic device layer is described in <Second Embodiment B> below.

[0676] <First Embodiment B>

[0677] The laminate having a semiconductor substrate is used for processing the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to the support substrate. After the processing of the semiconductor substrate, light is irradiated on the adhesive layer, and then the semiconductor substrate is separated from the support substrate.

[0678] As the semiconductor substrate, the semiconductor substrate described in <First Embodiment A> can be cited.

[0679] As the support substrate, the support substrate described in <First Embodiment A> can be cited.

[0680] <<Adhesive Layer>>

[0681] The adhesive layer is a layer formed of an adhesive composition.

[0682] The adhesive layer is provided between the semiconductor substrate and the support substrate.

[0683] The adhesive layer can be in contact with the support substrate or in contact with the semiconductor substrate.

[0684] The adhesive layer is formed using the adhesive composition for photoirradiation peeling of the present invention described above.

[0685] The adhesive composition of the present invention can be suitably used for forming an adhesive layer of a laminate having: a semiconductor substrate, a support substrate, and an adhesive layer provided between the semiconductor substrate and the support substrate. The laminate is used for: peeling the semiconductor substrate from the support substrate after the adhesive layer absorbs light irradiated from the support substrate side.

[0686] One of the characteristics of the adhesive layer obtained from the adhesive composition of the present invention is that the semiconductor substrate and the support substrate can be easily peeled after light irradiation.

[0687] When forming the adhesive layer from the adhesive composition, it is considered that the novolak resin reacts with the epoxy resin containing a siloxane skeleton.

[0688] The thickness of the adhesive layer is not particularly limited, and is usually 1 to 500 μm. From the viewpoint of maintaining the film strength, it is preferably 1.5 μm or more, more preferably 2 μm or more, still more preferably 3 μm or more. From the viewpoint of avoiding non-uniformity caused by a thick film, it is preferably 500 μm or less, more preferably 200 μm or less, still more preferably 100 μm or less, and further preferably 50 μm or less.

[0689] The thickness of the adhesive layer can be measured, for example, by using an optical or contact type film thickness meter.

[0690] Regarding the method for forming the adhesive layer from the adhesive composition, it is described in detail in the explanation part of <<Manufacturing method of an example of the laminate in the first embodiment B>> described below.

[0691] Hereinafter, an example of the configuration of the laminate of the first embodiment B will be described with reference to the drawings.

[0692] Figure 8 The laminate sequentially has: a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4.

[0693] The adhesive layer 2 is provided between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with the semiconductor substrate 1 and the support substrate 4.

[0694] <<Manufacturing method of an example of the laminate in the first embodiment B>>

[0695] Taking the laminate in the first embodiment B as an example, Figure 8 The manufacturing method of the laminate will be described below.

[0696] An example of the laminate of the present invention can be manufactured, for example, by a method including the following first process B to second process B.

[0697] First process B: A process of applying an adhesive composition onto a semiconductor substrate to form an adhesive coating layer.

[0698] Second process B: A process of heating the adhesive coating layer to form an adhesive layer.

[0699] The coating method of the adhesive composition is not particularly limited, and is usually a spin coating method. It should be noted that a method of separately forming a coating film by a spin coating method or the like, forming a sheet-like coating film, and pasting the sheet-like coating film as the adhesive coating layer can be adopted.

[0700] The heating temperature of the coated adhesive composition varies depending on the type and amount of the adhesive component contained in the adhesive composition, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., and thus cannot be generally specified. From the viewpoint of reproducibly achieving an appropriate adhesive layer, it is 80°C or higher and 300°C or lower. The heating time is usually appropriately determined within the range of 10 seconds to 10 minutes according to the heating temperature. The heating temperature is preferably 100°C or higher and 280°C or lower, more preferably 150°C or higher and 250°C or lower. The heating time is preferably 30 seconds or longer and 8 minutes or shorter, more preferably 1 minute or longer and 5 minutes or shorter.

[0701] Heating can be performed using a hot plate, an oven, or the like.

[0702] Usually, the coated adhesive composition is heated.

[0703] The film thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it if necessary is usually about 1 to 500 μm, and is appropriately determined so as to finally fall within the range of the thickness of the above-mentioned adhesive layer.

[0704] In the present invention, a laminate of the present invention can be obtained by applying a load in the thickness direction of the semiconductor substrate and the support substrate while performing a heat treatment or a pressure reduction treatment or both, and then performing a post-heat treatment. It should be noted that any of the treatment conditions of heat treatment, pressure reduction treatment, or both are appropriately determined based on various situations such as the type of the adhesive composition, the film thickness, and the obtained adhesive strength.

[0705] From the viewpoint of removing the solvent from the composition, etc., the heat treatment is generally appropriately determined within the range of 20 to 160°C. In particular, from the viewpoints of suppressing or avoiding excessive curing and unnecessary deterioration of the adhesive component, it is preferably 150°C or lower, more preferably 130°C or lower. The heating time is appropriately determined according to the heating temperature and the type of adhesive. From the viewpoint of reliably achieving appropriate adhesion, it is generally 30 seconds or longer, preferably 1 minute or longer. From the viewpoint of suppressing the deterioration of the adhesive layer and other members, it is generally 10 minutes or shorter, preferably 5 minutes or shorter.

[0706] The pressure reduction treatment only needs to expose the adhesive coating layers in contact with each other to an air pressure of 10 to 10,000 Pa. The time for the pressure reduction treatment is generally 1 to 30 minutes.

[0707] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not have an adverse effect on the semiconductor substrate, the support substrate, and the layers therebetween, and can firmly bond them together, and is generally in the range of 10 to 50,000 N.

[0708] From the viewpoints of achieving a sufficient curing rate, etc., the temperature of the post-heating is preferably 120°C or higher. From the viewpoints of preventing the deterioration of the substrate and each layer, etc., the temperature of the post-heating is preferably 260°C or lower.

[0709] From the viewpoint of achieving appropriate bonding between the substrate and the layer constituting the laminate, the time for the post-heating is generally 1 minute or longer, preferably 5 minutes or longer. From the viewpoints of suppressing or avoiding adverse effects on each layer caused by excessive heating, etc., the time for the post-heating is generally 180 minutes or shorter, preferably 120 minutes or shorter.

[0710] The post-heating can be performed using a hot plate, an oven, etc. In the case of performing the post-heating using a hot plate, the semiconductor substrate and the support substrate of the laminate can be heated with either one facing down. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferable to heat with the semiconductor substrate facing down.

[0711] It should be noted that one of the purposes of the post-heating treatment is to form an adhesive layer as a more appropriate self-supporting film.

[0712] Hereinafter, Figures 9A - 9B is used to Figure 8 illustrate an example of a method for manufacturing

[0713] Figures 9A - 9B is a diagram for illustrating one embodiment of the manufacturing of the laminate.

[0714] First, a laminate having an adhesive coating layer 2a formed on a semiconductor substrate 1 is prepared (Figure 9A )。This laminate can be obtained, for example, by applying the adhesive composition onto the semiconductor substrate 1 and heating it.

[0715] Next, Figure 9A The laminate shown and the support substrate 4 are bonded together in such a way that the adhesive-coated layer 2a is in contact with the support substrate 4. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is disposed on the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive-coated layer 2a, and the adhesive-coated layer 2a is heated by the heating device to cure it and transform it into the adhesive layer 2( Figure 9B ).

[0716] By Figures 9A - 9B the process shown in, the laminate shown in Figure 8 can be obtained.

[0717] It should be noted that as long as the effects of the present invention are not impaired, the application and heating of the adhesive composition can be carried out sequentially on either substrate.

[0718] <<Second Embodiment B>>

[0719] The laminate having the electronic device layer is used for processing the electronic device layer. During the processing of the electronic device layer, the electronic device layer is bonded to the support substrate. After the processing of the electronic device layer, light is irradiated onto the adhesive layer, and then the electronic device layer is separated from the support substrate.

[0720] <<Electronic Device Layer>>

[0721] As the electronic device layer, the same electronic device layer as described in the <<Electronic Device Layer>> section of the above <Second Embodiment A> can be exemplified.

[0722] <<Support Substrate>>

[0723] As the support substrate, the same support substrate as described in the <<Support Substrate>> section of the above <First Embodiment A> can be exemplified.

[0724] <<Adhesive Layer>>

[0725] The adhesive layer is formed using the above-described adhesive composition for photoirradiation peeling of the present invention.

[0726] The detailed description of the adhesive layer is as described in the <<Adhesive Layer>> section of the above <First Embodiment B>.

[0727] An example of the configuration of the laminate of the second embodiment B will be described below with reference to the drawings.

[0728] Figure 10 Schematic cross-sectional view showing an example of the laminate of the second embodiment B.

[0729] Figure 10 The laminate sequentially includes: a support substrate 24, an adhesive layer 22, and an electronic device layer 26.

[0730] The electronic device layer 26 includes: a plurality of semiconductor chip substrates 21 and a sealing resin 25 as a sealing material disposed between the semiconductor chip substrates 21.

[0731] The adhesive layer 22 is provided between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with the electronic device layer 26 and the support substrate 24.

[0732] <<Manufacturing method of an example of the laminate in the second embodiment B>>

[0733] Taking the laminate shown in the laminate of the second embodiment B as an example, the manufacturing method of the laminate will be described below. Figure 10 Taking the laminate shown in the laminate of the second embodiment B as an example, the manufacturing method of the laminate will be described below.

[0734] The laminate of the present invention can be manufactured, for example, by a method including the following first process B to fourth process B.

[0735] First process B: A process of applying an adhesive composition to the surface of the support substrate to form an adhesive coating layer (if necessary, further heating to form an adhesive layer).

[0736] Second process B: A process of placing the semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and bonding the semiconductor chip substrate to the adhesive coating layer or the adhesive layer while performing at least any one of heat treatment and pressure reduction treatment.

[0737] Third process B: A process of curing the adhesive coating layer by post-heat treatment to form an adhesive layer.

[0738] Fourth process B: A process of sealing the semiconductor chip substrate fixed on the adhesive layer with a sealing resin.

[0739] If the second process B is described in more detail, for example, the process of the following embodiment (iB) can be cited.

[0740] (iB) Place the semiconductor chip substrate on the adhesive coating layer or the adhesive layer, and while performing at least one of heat treatment and pressure reduction treatment, apply a load in the thickness direction of the semiconductor chip substrate and the support substrate to make them fit, and bond the semiconductor chip substrate to the adhesive coating layer or the adhesive layer.

[0741] It should be noted that the third process B can be carried out after the semiconductor chip substrate is bonded to the adhesive coating layer in the second process B, or it can also be carried out together with the second process B. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer can be heated to cure it, thereby simultaneously achieving the close adhesion of the semiconductor chip substrate to the adhesive coating layer and the curing from the adhesive coating layer to the adhesive layer, and bonding the adhesive layer to the semiconductor chip substrate.

[0742] In addition, the third process B can be carried out before the second process B, or the semiconductor chip substrate can be placed on the adhesive layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive layer can be bonded to the semiconductor chip substrate.

[0743] The coating method, the heating temperature of the adhesive composition after coating, the heating method, etc. are as described in the above <Manufacturing method of an example of the laminate in the first embodiment B> of the above <First embodiment B>.

[0744] Regarding the manufacturing method of the laminate of the second embodiment B, the sequence will be further described in detail below with reference to the drawings. In this manufacturing method, the Figure 10 laminate shown is manufactured.

[0745] As Figure 11A shown, an adhesive coating layer 22' formed of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' can also be heated to form an adhesive layer 22.

[0746] Next, as Figure 11B shown, the semiconductor chip substrate 21 is placed on the adhesive layer 22 or the adhesive coating layer 22', and while performing at least one of heat treatment and decompression treatment, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to make it closely adhere, and the semiconductor chip substrate 21 is bonded to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is bonded to the adhesive coating layer 22', the adhesive coating layer 22' is post-heated to cure it to form an adhesive layer 22, and the semiconductor chip substrate 21 is fixed to the adhesive layer 22.

[0747] Next, as Figure 11C shown, the semiconductor chip substrate 21 fixed on the adhesive layer 22 is sealed with a sealing resin 25. In Figure 11CAmong them, a plurality of semiconductor chip substrates 21 temporarily bonded to a support substrate 24 via an adhesive layer 22 are sealed with a sealing resin 25. An electronic device layer 26 having the semiconductor chip substrates 21 and the sealing resin 25 disposed between the semiconductor chip substrates 21 is formed on the adhesive layer 22. Thus, the electronic device layer 26 becomes a base material layer in which a plurality of semiconductor chip substrates are embedded in the sealing resin.

[0748] <<<Sealing process>>>

[0749] The semiconductor chip substrates 21 are sealed using a sealing material.

[0750] As the sealing material for sealing the semiconductor chip substrates 21, a member that can insulate or seal a member made of metal or semiconductor is used.

[0751] In the present invention, as the sealing material, for example, a resin composition (sealing resin) is used. As the type of the sealing resin, as long as it can seal and / or insulate metal or semiconductor, there is no particular limitation. For example, an epoxy resin or a silicone resin is preferably used.

[0752] In addition to the resin component, the sealing material may further contain other components such as fillers. As the filler, for example, spherical silica particles can be cited.

[0753] In the sealing process, for example, a sealing resin heated to 130 to 170 °C is supplied onto the adhesive layer 22 in a state of maintaining a high viscosity and covering the semiconductor chip substrates 21, and compression molding is performed, whereby a layer formed of the sealing resin 25 is formed on the adhesive layer 22. At this time, the temperature condition is, for example, 130 to 170 °C. In addition, the pressure applied to the semiconductor chip substrates 21 is, for example, 50 to 500 N / cm 2 .

[0754] (Manufacturing method of processed semiconductor substrate or electronic device layer)

[0755] If the laminate of the present invention is used, a manufacturing method of a processed semiconductor substrate or a manufacturing method of a processed electronic device layer can be provided.

[0756] The "manufacturing method of a processed semiconductor substrate" uses the laminate described in the column of the above <First Embodiment B> of the above (laminate). In addition, the "manufacturing method of a processed electronic device layer" uses the laminate described in the column of the above <Second Embodiment B> of the above (laminate).

[0757] The "manufacturing method of a processed semiconductor substrate" will be described in the following <Third Embodiment B>, and the "manufacturing method of a processed electronic device layer" will be described in the following <Fourth Embodiment B>.

[0758] <Third Embodiment B>

[0759] The method for manufacturing a processed semiconductor substrate of the present invention includes: the following 5A process B and the following 6A process B. The method for manufacturing a processed semiconductor substrate may further include the following 7A process B.

[0760] Here, the 5A process B is a process B for processing the semiconductor substrate in the laminate described in the column of <First Embodiment B> above.

[0761] In addition, the 6A process B is a process of separating the semiconductor substrate processed by the 5A process B from the support substrate.

[0762] In addition, the 7A process B is a process of cleaning the processed semiconductor substrate after the 6A process B.

[0763] The processing performed on the semiconductor substrate in the 5A process B is, for example, processing on the side opposite to the circuit surface of the wafer, and examples include thinning of the wafer by grinding the back surface of the wafer. Then, for example, the formation of through-silicon vias (TSVs) etc. is performed, and then the thinned wafer is peeled off from the support substrate to form a laminate of wafers for three-dimensional mounting. In addition, for example, the formation of back surface electrodes of the wafer etc. is also performed before and after three-dimensional mounting. Heat of about 250 to 350 °C is applied in a state of being bonded to the support substrate during the thinning of the wafer and the TSV process. The laminate of the present invention usually includes an adhesive layer and has heat resistance against the applied heat.

[0764] The processing performed on the semiconductor substrate in the 5A process B may also be a process of dicing (singulating) the semiconductor substrate.

[0765] It should be noted that the processing is not limited to the above processing, and for example, it also includes the mounting process of semiconductor components etc. in the case of temporarily bonding to the support substrate in order to support the substrate for mounting semiconductor components.

[0766] In the 6A process B, examples of the method for separating (peeling) the semiconductor substrate from the support substrate include: after light irradiation of the adhesive layer, mechanical peeling using a tool with a sharp part, peeling by tearing between the support and the semiconductor wafer, etc., but it is not limited thereto.

[0767] By irradiating light on the adhesive layer from the support substrate side, deterioration of the adhesive layer (for example, separation or decomposition of the adhesive layer) occurs as described above, and then, for example, by pulling up either substrate, the semiconductor substrate can be easily separated from the support substrate.

[0768] Irradiation of the adhesive layer with light does not necessarily need to be performed on the entire area of the adhesive layer. Even if areas irradiated with light and areas not irradiated with light are mixed, as long as the peelability of the adhesive layer as a whole is sufficiently improved, the semiconductor substrate can be separated from the support substrate by a slight external force such as pulling up the support substrate. The ratio and positional relationship between the area irradiated with light and the area not irradiated with light vary depending on the type of adhesive used, its specific composition, the thickness of the adhesive layer, the intensity of the irradiated light, etc. However, for those skilled in the art, appropriate conditions can be set without excessive experimentation. Due to such circumstances, in the manufacturing method of the processed semiconductor substrate according to the present invention, for example, when the support substrate of the laminate used has light transmissivity, the light irradiation time can be shortened when peeling is performed by light irradiation from the support substrate side. As a result, not only an improvement in throughput can be expected, but also physical stress for peeling can be avoided, and the semiconductor substrate can be easily and efficiently separated from the support substrate only by light irradiation.

[0769] Generally, the irradiation amount of light for peeling is 50 to 3000 mJ / cm 2 . The irradiation time is appropriately determined according to the wavelength and irradiation amount.

[0770] The wavelength of the light for peeling is preferably a wavelength of 250 to 600 nm, more preferably a wavelength of 250 to 370 nm, as described above. More appropriate wavelengths are 308 nm, 343 nm, 355 nm, 365 nm, or 532 nm. The irradiation amount of light required for peeling is an irradiation amount that causes appropriate deterioration of the novolac resin, such as decomposition.

[0771] The light for peeling can be a laser or non-laser light emitted from a light source such as an ultraviolet lamp.

[0772] A cleaning agent composition can be sprayed on the surface of at least any one of the separated semiconductor substrate and the support substrate, or the separated semiconductor substrate or the support substrate can be immersed in the cleaning agent composition to clean the substrate.

[0773] In addition, a tape or the like can be used to clean the surface of the processed semiconductor substrate or the like.

[0774] As an example of cleaning the substrate, a 7A process B of cleaning the processed semiconductor substrate can be performed after the 6A process B.

[0775] Examples of the cleaning agent composition for cleaning include the substances described in the above <Third Embodiment A>.

[0776] Regarding the constituent elements and method elements related to the above-described processes of Embodiment B of the method for manufacturing a processed semiconductor substrate of the present invention, various modifications can be made as long as they do not depart from the gist of the present invention.

[0777] Embodiment B of the method for manufacturing a processed semiconductor substrate of the present invention may also include processes other than the above-described processes.

[0778] In the peeling method of the present invention, when the semiconductor substrate or the support substrate of the laminate of the present invention has translucency, the semiconductor substrate of the laminate is separated from the support substrate by irradiating the adhesive layer with light from the semiconductor substrate side or the support substrate side.

[0779] In one example of the laminate of the present invention, the semiconductor substrate and the support substrate are temporarily bonded appropriately and peelably through an adhesive layer. Therefore, for example, when the support substrate has translucency, the semiconductor substrate can be easily separated from the support substrate by irradiating the adhesive layer with light from the support substrate side of the laminate. Usually, peeling is performed after processing the semiconductor substrate of the laminate.

[0780] Use Figures 12A - 12D An example of the third Embodiment B will be described. This example is an example of manufacturing a thinned semiconductor substrate.

[0781] First, a laminate ( Figure 12A ) is prepared. This laminate is the same laminate as the laminate shown in Figure 8 and Figure 9B .

[0782] Next, using a grinding device (not shown), the surface of the semiconductor substrate 1 opposite to the surface in contact with the adhesive layer 2 is ground to thin the semiconductor substrate 1 ( Figure 12B ). It should be noted that formation of a through electrode or the like may be performed on the thinned semiconductor substrate 1.

[0783] Next, after irradiating the adhesive layer 2 with light from the support substrate 4 side, using a peeling device (not shown), the thinned semiconductor substrate 1 is separated from the support substrate 4 ( Figure 12C ).

[0784] In this way, a thinned semiconductor substrate 1 ( Figure 12D ) is obtained.

[0785] Here, residues of the adhesive layer 2 sometimes remain on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 using a cleaning agent composition to remove the residues of the adhesive layer 2 from the semiconductor substrate 1.

[0786] <Fourth Embodiment B>

[0787] The manufacturing method of the processed electronic device layer of the present invention includes: the following 5B process B and the following 6B process B. The manufacturing method of the processed electronic device layer may further include the following 7B process B.

[0788] Herein, the 5B process B is a process B for processing the electronic device layer in the laminate described in the column of the above <Second Embodiment B>.

[0789] In addition, the 6B process B is a process for separating the electronic device layer processed by the 5B process B from the support substrate.

[0790] In addition, the 7B process B is a process for cleaning the processed electronic device layer after the 6B process B.

[0791] Hereinafter, Figures 13A - 13F a specific example of the Fourth Embodiment B will be described.

[0792] Examples of the processing performed on the electronic device layer in the 5B process B include a grinding process, a wiring layer formation process, and the like.

[0793] <<Grinding Process>>

[0794] The grinding process is a process for grinding the resin portion of the layer of the sealing resin 25 in the electronic device layer 26 in such a manner that a part of the semiconductor chip substrate 21 is exposed.

[0795] The grinding of the sealing resin portion is performed, for example, as Figure 13B shown, by grinding the layer of the sealing resin 25 of the laminate shown to be substantially the same thickness as the semiconductor chip substrate 21. It should be noted that Figure 13A the laminate shown is the same laminate as the laminates shown in Figure 13A and Figure 10 and Figure 11C shown.

[0796] <<Wiring Layer Formation Process>>

[0797] The wiring layer formation process is a process for forming a wiring layer on the exposed semiconductor chip substrate 21 after the above grinding process.

[0798] Figure 13C In

[0799] The wiring layer 28, also known as the RDL (Redistribution Layer), is a wiring body of a thin film that constitutes the wiring connected to the substrate and can have a single-layer or multi-layer structure. The wiring layer 28 can be a layer formed by forming wiring between dielectrics (such as silicon oxide (SiO X ), photosensitive resins such as photosensitive epoxy resin, etc.) using a conductor (such as metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloy), but is not limited thereto.

[0800] As a method for forming the wiring layer 28, for example, the methods listed in the <Wiring Layer Formation Process> of the above <Fourth Embodiment A> can be cited.

[0801] In the manufacturing method of the laminate of the Fourth Embodiment B, bumps can be further formed or components can be mounted on the wiring layer 28. The mounting of components on the wiring layer 28 can be performed using, for example, a chip mounter.

[0802] The laminate of the Fourth Embodiment B can be a laminate manufactured in the process based on the following technology: a fan-out technology in which the terminals provided on the semiconductor chip substrate are mounted on a wiring layer extending outside the chip region.

[0803] In the 6B process B, examples of the method for separating (peeling) the electronic device layer from the support substrate include: mechanical peeling using a tool with a sharp part after light irradiation of the adhesive layer, peeling by tearing between the support and the electronic device layer, etc., but are not limited thereto.

[0804] By irradiating light on the adhesive layer from the support substrate side, as described above, the adhesive layer deteriorates (for example, separation or decomposition of the adhesive layer), and then, for example, by pulling up either substrate, the electronic device layer can be easily separated from the support substrate.

[0805] Figures 13D - 13E It is a schematic cross-sectional view for explaining the separation method of the laminate, Figure 13F It is a schematic cross-sectional view for explaining the cleaning method after the separation of the laminate. Through Figures 13D - 13F , an embodiment of the manufacturing method of the semiconductor package (electronic component) can be explained.

[0806] As Figure 13D shown, the process of separating the laminate is a process of irradiating light (arrow) on the adhesive layer 22 through the support substrate 24 to deteriorate the adhesive layer 22, thereby separating the electronic device layer 26 from the support substrate 24.

[0807] After irradiating light (arrow) on the adhesive layer 22 to deteriorate the adhesive layer 22, as Figure 13E shown, the support substrate 24 is separated from the electronic device layer 26.

[0808] Regarding the irradiation conditions, irradiation methods, etc. of the light irradiation on the adhesive layer 22, as described in the column of <Third Embodiment B> above.

[0809] The cleaning agent composition can be sprayed on the surface of at least any one of the separated electronic device layer and the support substrate, or the separated electronic device layer or the support substrate can be immersed in the cleaning agent composition to clean the substrate.

[0810] In addition, a tape or the like can be used to clean the surface of the processed electronic device layer or the like.

[0811] For example, in Figure 13E , after the separation step, the adhesive layer 22 is attached to the electronic device layer 26. By using a cleaning agent composition such as an acid or a base, the adhesive layer 22 can be decomposed and the adhesive layer 22 can be removed. By removing the adhesive layer, a processed electronic device layer (electronic component) as shown in Figure 13F can be appropriately obtained.

[0812] Regarding the constituent elements and method elements related to the above-described steps of the manufacturing method of the processed electronic device layer of the present invention, various modifications can be made as long as they do not depart from the gist of the present invention.

[0813] Embodiment B of the manufacturing method of the processed electronic device layer of the present invention may also include steps other than the above-described steps.

[0814] In Embodiment B of the laminate of the present invention, the electronic device layer and the support substrate are temporarily bonded appropriately and peelably via the adhesive layer. Therefore, for example, when the support substrate has light transmissivity, the electronic device layer can be easily separated from the support substrate by irradiating light on the adhesive layer from the support substrate side of the laminate. Usually, the peeling is performed after processing the electronic device layer of the laminate.

[0815] Examples

[0816] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples. It should be noted that the devices used are as follows.

[0817] (First Example)

[0818] The following describes an example of the release agent composition of the present invention as the first example.

[0819] [Device]

[0820] (1) Stirrer: Planetary mixer ARE-500 manufactured by THINKY Corporation.

[0821] (2) Vacuum lamination device: XBS300 manufactured by SUSS MicroTec Co., Ltd.

[0822] (3) Cutting machine: SS30 manufactured by Tokyo Seimitsu Co., Ltd.

[0823] (4) Optical film thickness meter (film thickness measurement): F-50 manufactured by Filmetrics Co., Ltd.

[0824] (5) Laser irradiation device: Lambda SX manufactured by Coherent Co., Ltd.

[0825] [A1] Preparation of adhesive composition

[0826] [Preparation Example A1]

[0827] 80 g of MQ resin containing polysiloxane and vinyl (manufactured by Wacker Chemie AG), 2.52 g of linear polydimethylsiloxane with SiH group and viscosity of 100 mPa·s (manufactured by Wacker Chemie), 5.89 g of linear polydimethylsiloxane with SiH group and viscosity of 70 mPa·s (manufactured by Wacker Chemie AG), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie AG) were added to a 600 mL stirring container dedicated to a stirrer, and stirred with a stirrer for 5 minutes to obtain a mixture (I).

[0828] 0.147 g of a platinum catalyst (manufactured by Wacker Chemie AG) and 5.81 g of linear polydimethylsiloxane with vinyl group and viscosity of 1000 mPa·s (manufactured by Wacker Chemie AG) were stirred with a stirrer for 5 minutes to obtain a mixture (II).

[0829] 3.96 g of the mixture (II) was added to the mixture (I), and stirred with a stirrer for 5 minutes to obtain a mixture (III).

[0830] Finally, the obtained mixture (III) was filtered through a 300-mesh nylon filter to obtain an adhesive composition. The viscosity of the adhesive composition measured with a viscometer was 10000 mPa·s.

[0831] [A2] Preparation of cleaning agent composition

[0832] [Preparation Example A2]

[0833] 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.) was mixed with 95 g of N-methyl-2-pyrrolidone and stirred well to obtain a cleaning agent composition.

[0834] [A3] Synthesis of novolak resin

[0835] [Synthesis Example A1]

[0836] Into a flask, 10.0 g of 2,2'-dihydroxybiphenyl, 4.19 g of 1-naphthaldehyde, 6.24 g of 1-pyrenecarboxaldehyde, 77 g of methanesulfonic acid, and 49.48 g of propylene glycol monomethyl ether acetate as a solvent were added, and reflux stirring was carried out overnight under a nitrogen atmosphere. After allowing the resulting reaction mixture to cool, 96 g of tetrahydrofuran was added for dilution, and the resulting diluted solution was dropped into methanol, whereby a precipitate was obtained. The precipitate obtained was recovered by filtration, the filter cake was washed with methanol, and dried under reduced pressure at 60 °C, whereby a novolak resin was obtained. The result measured by the following method was that the weight-average molecular weight of the novolak resin as a polymer was 5300.

[0837] The weight-average molecular weight was measured using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by Tosoh Corporation) and GPC columns (Shodex KF-803L, Shodex KF-802, and Shodex KF-801 manufactured by Showa Denko K.K. in this order), setting the column temperature at 40 °C, using tetrahydrofuran as an eluent (dissolution solvent), setting the flow rate at 1.00 mL / minute, and using polystyrene (manufactured by Sigma Aldrich) as a standard sample.

[0838] The obtained novolak resin has the following repeating units.

[0839]

[0840] [Synthesis Example A2]

[0841] Into a flask, 10.0 g of carbazole, 7.69 g of p-formylbenzoic acid, 0.74 g of methanesulfonic acid, and 42.99 g of propylene glycol monomethyl ether acetate as a solvent were added, and heating and stirring were carried out at 120 °C overnight under a nitrogen atmosphere. After allowing the resulting reaction mixture to cool, 96 g of tetrahydrofuran was added for dilution, and the resulting diluted solution was dropped into methanol, whereby a precipitate was obtained. The precipitate obtained was recovered by filtration, the filter cake was washed with methanol, and dried under reduced pressure at 60 °C, whereby a novolak resin was obtained. The result measured by the following method was that the weight-average molecular weight of the novolak resin as a polymer was 9300.

[0842] The weight-average molecular weight was measured using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by TOSOH CORPORATION) and GPC columns (Shodex KF-803L, Shodex KF-802, and Shodex KF-801, manufactured by Showa Denko K.K. in this order). The column temperature was set at 40°C, tetrahydrofuran was used as the eluent (dissolution solvent), the flow rate was set at 1.00 mL / minute, and polystyrene (manufactured by Sigma Aldrich) was used as the standard sample for the measurement.

[0843] The obtained novolak resin has the following repeating unit.

[0844]

[0845] [Synthesis Example A3]

[0846] 7.4 g of tert-butoxystyrene, 7.38 g of 4-pentyloxybenzaldehyde, and 10.0 g of propylene glycol monomethyl ether as a solvent were added to a flask and stirred. After stirring, 10.0 g of N,N'-diphenyl-1,4-phenylenediamine, 1.1 g of methanesulfonic acid, and 31.1 g of propylene glycol monomethyl ether as a solvent were added, and the mixture was heated and stirred at 110°C overnight under a nitrogen atmosphere. Propylene glycol monomethyl ether acetate and pure water were added to the reaction solution and stirred. Then, liquid separation treatment was performed, the organic layer was recovered, and concentrated to obtain a novolak resin. As a result of measurement by the following method, the weight-average molecular weight of the novolak resin as a polymer was 1200.

[0847] The weight-average molecular weight was measured using a GPC apparatus (EcoSEC, HLC-8220GPC manufactured by TOSOH CORPORATION) and GPC columns (Shodex KF-803L, Shodex KF-802, and Shodex KF-801, manufactured by Showa Denko K.K. in this order). The column temperature was set at 40°C, tetrahydrofuran was used as the eluent (dissolution solvent), the flow rate was set at 1.00 mL / minute, and polystyrene (manufactured by Sigma Aldrich) was used as the standard sample for the measurement.

[0848]

[0849] [A4] Preparation of the release agent composition

[0850] [Preparation Example A3]

[0851] Dissolve 3.4 g of the novolak resin obtained in Synthesis Example A1, 0.4 g of epoxy-modified silicone KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent, and 0.4 g of epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.) in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. Filter the resulting solution through a polyethylene microfilter with a pore size of 0.2 μm to obtain Release Agent Composition 1.

[0852] [Preparation Example A4]

[0853] Dissolve 2.7 g of the novolak resin obtained in Synthesis Example A2 and 0.8 g of epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. Filter the resulting solution through a polyethylene microfilter with a pore size of 0.2 μm to obtain Release Agent Composition 2.

[0854] [Preparation Example A5]

[0855] Dissolve 3.3 g of the novolak resin obtained in Synthesis Example A1 and 0.7 g of epoxy-modified silicone EP-3400L (manufactured by ADEKA Corporation) as a crosslinking agent in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. Filter the resulting solution through a polyethylene microfilter with a pore size of 0.2 μm to obtain Release Agent Composition 3.

[0856] [Preparation Example A6]

[0857] Dissolve 3.7 g of the novolak resin obtained in Synthesis Example A1 and 0.4 g of epoxy-modified silicone KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. Filter the resulting solution through a polyethylene microfilter with a pore size of 0.2 μm to obtain Release Agent Composition 4.

[0858] [Preparation Example A7]

[0859] Dissolve 2.9 g of the novolak resin obtained in Synthesis Example A2 and 0.6 g of epoxy-modified silicone KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. Filter the resulting solution through a polyethylene microfilter with a pore size of 0.2 μm to obtain Release Agent Composition 5.

[0860] [Preparation Example A8]

[0861] 2.9 g of the novolak resin obtained in Synthesis Example A2 and 0.6 g of an epoxy-modified silicone EP-3400L (manufactured by ADEKA Corporation) as a crosslinking agent were dissolved in 23.3 g of propylene glycol monomethyl ether acetate and 23.3 g of propylene glycol monomethyl ether as solvents, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition 6.

[0862] [Preparation Example A9]

[0863] 3.3 g of the novolak resin obtained in Synthesis Example A2 and 0.7 g of 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane as a crosslinking agent were dissolved in 23.3 g of propylene glycol monomethyl ether acetate and 23.3 g of propylene glycol monomethyl ether as solvents, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition 7.

[0864] [Preparation Example A10]

[0865] 3.3 g of the novolak resin obtained in Synthesis Example A1, 0.3 g of an epoxy-modified silicone KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.3 g of an epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.03 g of 2-phenyl-1-benzyl-1H-imidazole as a curing catalyst were dissolved in 46.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition 8.

[0866] [Preparation Example A11]

[0867] 3.6 g of the novolak resin obtained in Synthesis Example A1, 0.4 g of an epoxy-modified silicone KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.04 g of 2-phenyl-1-benzyl-1H-imidazole as a curing catalyst were dissolved in 46.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a release agent composition 9.

[0868] [Preparation Example A12]

[0869] 3.6 g of the novolak resin obtained in Synthesis Example A1, 0.4 g of an epoxy-modified silicone KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent, and 0.04 g of tetrabutylammonium bromide as a curing catalyst were dissolved in 23.3 g of propylene glycol monomethyl ether acetate and 23.3 g of propylene glycol monomethyl ether as solvents. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition 10.

[0870] [Preparation Example A13]

[0871] 2.7 g of the novolak resin obtained in Synthesis Example A3 and 0.3 g of an epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent were dissolved in 27.0 g of propylene glycol monomethyl ether acetate as a solvent. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition 11.

[0872] [Comparative Preparation Example A1]

[0873] 4.0 g of the novolak resin obtained in Synthesis Example A1 was dissolved in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition 12.

[0874] [Comparative Preparation Example A2]

[0875] 3.6 g of the novolak resin obtained in Synthesis Example A1 and 0.4 g of a phenylmethyl silicone KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent were dissolved in 46.0 g of propylene glycol monomethyl ether acetate as a solvent. The resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain a stripping agent composition 13.

[0876] The structures of the crosslinking agents used in the first and second embodiments are shown below.

[0877] Epoxy-modified silicone KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0878]

[0879] Epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0880]

[0881] Epoxy-modified silicone EP-3400L (manufactured by ADEKA Corporation)

[0882]

[0883] Epoxy-modified silicone KR-470 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0884]

[0885] 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane

[0886]

[0887] [A5] Confirmation of removability of the film

[0888] [Example A1-1]

[0889] The release agent composition 1 obtained in Preparation Example A3 was spin-coated on a 4-inch bare silicon wafer to a final film thickness of 200 nm, and heated at 250 °C for 5 minutes to form a film on the bare silicon wafer. Substrates with the film formed were produced in the quantities required for evaluation.

[0890] [Examples A1-2 to A1-5]

[0891] The release agent compositions 2 to 5 obtained in Preparation Examples A4 to A7 were used respectively to replace the release agent composition 1 obtained in Preparation Example A3, and otherwise, films were formed on the bare silicon wafers by the same method as in Example A1.

[0892] [Example A1-6]

[0893] The release agent composition 6 obtained in Preparation Example A8 was spin-coated on a 4-inch bare silicon wafer to a final film thickness of 200 nm, and heated at 230 °C for 30 minutes to form a film on the bare silicon wafer.

[0894] [Example A1-7]

[0895] The release agent composition 7 obtained in Preparation Example A9 was spin-coated on a 4-inch bare silicon wafer to a final film thickness of 200 nm, and heated at 250 °C for 30 minutes to form a film on the bare silicon wafer.

[0896] [Examples A1-8 to A1-10]

[0897] The release agent compositions 8 to 10 obtained in Preparation Examples A10 to A12 were used respectively to replace the release agent composition 1 obtained in Preparation Example A3, and otherwise, films were formed on the bare silicon wafers by the same method as in Example A1.

[0898] [Example A1-11]

[0899] The release agent composition 11 obtained in Preparation Example A13 was spin-coated on a 4-inch bare silicon wafer to a final film thickness of 300 nm, and heated at 230 °C for 5 minutes to form a film on the substrate. Substrates with the formed film were produced in the required quantities.

[0900] [Comparative Examples A1-1 to A1-2]

[0901] The release agent compositions 12 and 13 obtained in Comparative Preparation Examples A1 and A2 were spin-coated on a 4-inch bare silicon wafer to a final film thickness of 200 nm, respectively, and heated at 250 °C for 30 minutes to form films on the bare silicon wafers.

[0902] The film thicknesses of the films obtained in Examples A1-1 to A1-11 and Comparative Examples A1-1 to A1-2 were measured (film thickness before immersion). Then, each film together with the substrate was immersed in 7 mL of the cleaning agent composition obtained in Preparation Example A2 for 5 minutes, dried with an air gun, and the film thickness of each film was measured again (film thickness after immersion). In addition, an OK73 diluent (composition: 70% propylene glycol monomethyl ether, 30% propylene glycol monomethyl ether acetate) (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used instead of the cleaning agent composition, and the same operation was performed except for this, and the film thickness was measured. The residual film ratio (%) based on immersion was calculated using the following formula.

[0903] Residual film ratio (%) = [Film thickness after immersion (nm) / Film thickness before immersion (nm)] × 100

[0904] The results are shown in Tables 1-1 and 1-2.

[0905] [Table 1-1]

[0906]

[0907] [Table 1-2]

[0908]

[0909] [A6] Manufacture of laminate

[0910] [Example A2-1]

[0911] The release agent composition 1 obtained in Preparation Example A3 was spin-coated on a 300 mm glass wafer (EAGLE-XG, manufactured by Corning Inc., thickness 700 μm) as the carrier-side substrate, and fired on a hot plate at 250 °C for 5 minutes to form a release agent coating layer on the glass wafer as the support substrate so that the film thickness in the finally obtained laminate became 200 nm.

[0912] The adhesive composition 1 obtained in Preparation Example A1 was spin-coated on the silicon wafer on the device wafer side to form an adhesive coating layer such that the film thickness in the finally obtained laminate became 60 μm.

[0913] Then, using a laminating device, the device wafer having the adhesive coating layer formed thereon was laminated with the support substrate on the carrier side having the release agent coating layer formed thereon in such a manner as to sandwich the adhesive coating layer and the release agent coating layer, and then post-heat treatment was performed at 200 °C for 10 minutes, whereby a laminate was produced. It should be noted that the lamination was performed at a temperature of 23 °C and a reduced pressure of 1500 Pa. It should be noted that the laminates were produced in required quantities.

[0914] <Evaluation of peelability and cleanability>

[0915] The silicon wafer of the obtained laminate was pasted onto a dicing tape (manufactured by Nitto Denko Corporation, DU-300) and fixed. The silicon wafer of the laminate fixed with the dicing tape was singulated into 4×4 cm chips using a dicing machine (manufactured by Tokyo Seimitsu Co., Ltd.).

[0916] Using a laser irradiation device, the release layer was irradiated with a laser having a wavelength of 308 nm from the glass wafer side of the singulated laminate at 200 mJ / cm 2 The lowest irradiation dose at which peeling occurred was taken as the optimum irradiation dose. Then, the release layer was irradiated with a laser having a wavelength of 308 nm at the optimum irradiation dose over the entire surface from the glass wafer side of the singulated laminate, and the support substrate was manually lifted to confirm whether peeling was possible. The case where peeling was possible was designated as "Yes", and the case where peeling was not possible was designated as "No". The results are shown in Table 2-1.

[0917] In addition, the singulated glass wafer after peeling was immersed in the cleaning agent composition prepared in Preparation Example A2 for 5 minutes, and the removability (cleanability) of the release agent layer was investigated. The glass surface was observed using an optical microscope, and the case where no residue after laser irradiation was observed was designated as "Yes", and the case where residue was observed was designated as "No". The results are shown in Table 2-1.

[0918] [Examples A2-2 to A2-5]

[0919] The release agent compositions 2 to 5 obtained in Preparation Examples A4 to A7 were respectively used in place of the release agent composition 1 obtained in Preparation Example A3, and except for this, laminates were produced in the same manner as in Example A2-1.

[0920] Evaluation was performed in the same manner as in Example A2-1. The results are shown in Table 2-1.

[0921] [Example A2-6]

[0922] The release agent composition 6 obtained in Preparation Example A8 was used to replace the release agent composition 1 obtained in Preparation Example A3, and the firing conditions after coating the release agent composition were changed to 30 minutes at 230°C. Except for the above two aspects, a laminate was produced by the same method as in Example A2-1.

[0923] Evaluation was carried out by the same method as in Example A2-1. The results are shown in Table 2-1.

[0924] [Example A2-7]

[0925] The release agent composition 7 obtained in Preparation Example A9 was used to replace the release agent composition 1 obtained in Preparation Example A3, and the firing conditions after coating the release agent composition were changed to 30 minutes at 250°C. Except for the above two aspects, a laminate was produced by the same method as in Example A2-1.

[0926] Evaluation was carried out by the same method as in Example A2-1. The results are shown in Table 2-2.

[0927] [Examples A2-8 to A2-10]

[0928] The release agent compositions 8 to 10 obtained in Preparation Examples A10 to A12 were respectively used to replace the release agent composition 1 obtained in Preparation Example A3. Except for this, a laminate was produced by the same method as in Example A2-1.

[0929] Evaluation was carried out by the same method as in Example A2-1. The results are shown in Table 2-2.

[0930] [Example A2-11]

[0931] The release agent composition 11 obtained in Preparation Example A13 was used to replace the release agent composition 1 obtained in Preparation Example A3, and the firing conditions after coating the release agent composition were changed to 5 minutes at 230°C. Except for the above two aspects, a laminate was produced by the same method as in Example A2-1.

[0932] Evaluation was carried out by the same method as in Example A2-1. The results are shown in Table 2-2.

[0933] [Comparative Examples A2-1 to A2-2]

[0934] The release agent compositions 12 to 13 obtained in Comparative Preparation Examples A1 to A2 were respectively used to replace the release agent composition 1 obtained in Preparation Example A3, and the firing conditions after coating the release agent composition were changed to 30 minutes at 250°C. Except for the above two aspects, a laminate was produced by the same method as in Example A2-1.

[0935] Evaluation was carried out in the same manner as in Example A2-1. The results are shown in Table 2-2.

[0936] [Table 2-1]

[0937]

[0938] [Table 2-2]

[0939]

[0940] (Second Embodiment)

[0941] Examples of the adhesive composition of the present invention are described below as the second embodiment.

[0942] [Apparatus]

[0943] (1) Vacuum laminating apparatus: XBS300 manufactured by SUSS MicroTec Co., Ltd.

[0944] (2) Inert gas oven: INL-60NI manufactured by KOYO THERMO SYSTEMS Co., Ltd.

[0945] (3) Laser irradiation apparatus: Lambda SX manufactured by Coherent Co., Ltd.

[0946] (4) Cutting machine: SS30 manufactured by Tokyo Seimitsu Co., Ltd.

[0947] [B1] Preparation of cleaning agent composition

[0948] [Preparation Example B1]

[0949] 5 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Chemical Co., Inc.) was mixed with 95 g of N-methyl-2-pyrrolidone and stirred well to obtain a cleaning agent composition.

[0950] [B2] Synthesis of novolac resin

[0951] [Synthesis Example B1]

[0952] 7.4 g of tert-butoxystyrene, 7.38 g of 4-pentyloxybenzaldehyde, and 10.0 g of propylene glycol monomethyl ether as a solvent were added to a flask and stirred. After stirring, 10.0 g of N,N'-diphenyl-1,4-phenylenediamine, 1.1 g of methanesulfonic acid, and 31.1 g of propylene glycol monomethyl ether as a solvent were added, and the mixture was heated and stirred at 110 °C overnight under a nitrogen atmosphere to obtain a reaction solution. Propylene glycol monomethyl ether acetate and pure water were added to the reaction solution and stirred. Then, liquid separation treatment was performed, the organic layer was recovered, and concentrated to obtain a novolak resin. As a result of measurement by the following method, the weight-average molecular weight of the novolak resin as a polymer was 1,200.

[0953] The weight-average molecular weight was measured using a GPC device (EcoSEC, HLC-8220GPC manufactured by TOSOH CORPORATION) and GPC columns (Shodex KF-803L, Shodex KF-802, and Shodex KF-801, all manufactured by Showa Denko K.K.) in order. The column temperature was set to 40 °C, tetrahydrofuran was used as an eluent (dissolution solvent), the flow rate was set to 1.00 mL / minute, and polystyrene (manufactured by Sigma Aldrich) was used as a standard sample.

[0954] The obtained novolak resin has the following repeating unit.

[0955]

[0956] [Synthesis Example B2]

[0957] 4.2 g of diphenylamine, 7.4 g of 3-hydroxydiphenylamine, 10.4 g of 2-ethylhexanal, 0.2 g of methanesulfonic acid, and 22.3 g of propylene glycol monomethyl ether acetate as a solvent were added to a flask, and the mixture was heated and stirred at 120 °C for 1 hour under a nitrogen atmosphere to obtain a reaction solution. Methanol was added to the reaction solution for dilution. The diluted solution was reprecipitated, and the solvent was distilled off to obtain a novolak resin. As a result of measurement by the following method, the weight-average molecular weight of the novolak resin as a polymer was 12,000.

[0958] The weight-average molecular weight was measured using a GPC device (EcoSEC, HLC-8220GPC manufactured by TOSOH CORPORATION) and GPC columns (Shodex KF-803L, Shodex KF-802, and Shodex KF-801, all manufactured by Showa Denko K.K.) in order. The column temperature was set to 40 °C, tetrahydrofuran was used as an eluent (dissolution solvent), the flow rate was set to 1.00 mL / minute, and polystyrene (manufactured by Sigma Aldrich) was used as a standard sample.

[0959] The obtained novolak resin has the following repeating units.

[0960]

[0961] [B3] Preparation of Adhesive Composition

[0962] [Preparation Example B2]

[0963] 11.5 g of the novolak resin obtained in Synthesis Example B1 and 3.5 g of an epoxy-modified silicone EP-3400L (manufactured by ADEKA Corporation) as a crosslinking agent were dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain Adhesive Composition 1.

[0964] [Preparation Example B3]

[0965] 11.5 g of the novolak resin obtained in Synthesis Example B1 and 3.5 g of an epoxy-modified silicone KF-1005 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent were dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain Adhesive Composition 2.

[0966] [Preparation Example B4]

[0967] 11.5 g of the novolak resin obtained in Synthesis Example B1 and 3.5 g of 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane as a crosslinking agent were dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain Adhesive Composition 3.

[0968] [Preparation Example B5]

[0969] 11.5 g of the novolak resin obtained in Synthesis Example B2 and 3.5 g of 1,3-bis[2-(7-oxabicyclo[4.1.0]heptan-3-yl)ethyl]-1,1,3,3-tetramethyldisiloxane as a crosslinking agent were dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain Adhesive Composition 4.

[0970] [Preparation Example B6]

[0971] 11.5 g of the novolak resin obtained in Synthesis Example B2 and 3.5 g of an epoxy-modified silicone KF-005 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a crosslinking agent were dissolved in 15.0 g of propylene glycol monomethyl ether acetate as a solvent, and the resulting solution was filtered through a polyethylene microfilter with a pore size of 0.2 μm to obtain Adhesive Composition 5.

[0972] [Comparative Preparation Example B1]

[0973] 80 g of an MQ resin (manufactured by Wacker Chemie) containing a polysiloxane backbone and vinyl groups, 2.52 g of a linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chemie), 5.89 g of a linear polydimethylsiloxane containing SiH groups with a viscosity of 70 mPa·s (manufactured by Wacker Chemie), and 0.22 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) were added to a 600 mL stirring container dedicated to a planetary mixer and stirred with a mixer for 5 minutes to obtain Mixture (I).

[0974] 0.147 g of a platinum catalyst (manufactured by Wacker Chemie) and 5.81 g of a linear polydimethylsiloxane containing vinyl groups with a viscosity of 1000 mPa·s (manufactured by Wacker Chemie) were stirred with a mixer for 5 minutes to obtain Mixture (II).

[0975] 3.96 g of Mixture (II) was added to the total amount of Mixture (I) and stirred with a mixer for 5 minutes to obtain Mixture (III). Finally, the obtained Mixture (III) was filtered through a 300-mesh nylon filter to obtain Adhesive Composition 6.

[0976] [B4] Lamination Test

[0977] [Example B1-1]

[0978] The Adhesive Composition 1 obtained in Preparation Example B2 was spin-coated on a 12-inch bare silicon wafer so that the film thickness in the finally obtained laminate became 3 μm to form an adhesive coating layer. Then, using a vacuum laminating device, the device wafer with the adhesive coating layer formed thereon was laminated with a 12-inch glass wafer (manufactured by Corning, thickness 700 μm) as a support substrate on the carrier side so as to sandwich the adhesive coating layer, and then heat-treated at 250 °C for 5 minutes to produce a laminate. It should be noted that the lamination was performed at a temperature of 23 °C and a reduced pressure of 1000 Pa. Laminates were produced in the required quantities for evaluation.

[0979] [Examples B1-2 to B1-5]

[0980] The adhesive compositions B2 to B5 obtained in Preparation Examples B3 to B6 were used to replace the adhesive composition 1 obtained in Preparation Example B2, and a laminate was produced in the same manner as in Example B1-1, except for this. In Examples B1-4 to B1-5, spin coating was performed so that the film thickness in the finally obtained laminate became 15 μm to form an adhesive coating layer, and evaluation was carried out.

[0981] [Comparative Example B1-1]

[0982] The adhesive composition 6 obtained in Comparative Preparation Example B1 was spin-coated on a 12-inch bare silicon wafer so that the film thickness in the finally obtained laminate became 3 μm to form an adhesive coating layer. Then, a laminate was produced in the same manner as in Example B1-1 using a vacuum laminating device.

[0983] The appearances of the laminates produced in Examples B1-1 to B1-5 and Comparative Example B1-1 were visually observed to confirm whether voids or delamination occurred. When no voids or delamination occurred, it was judged that the lamination of the laminate was good. The results are shown in Table 3.

[0984] [Table 3]

[0985]

[0986] [B5] Heat resistance test

[0987] [Example B2-1]

[0988] The laminate produced in Example B1-1 was placed in an inert gas oven and subjected to a heat treatment at 260 °C for 12 hours.

[0989] [Examples B2-2 to B2-5]

[0990] The laminates produced in Examples B1-2 to B1-5 were placed in an inert gas oven and subjected to a heat treatment under the same conditions as in Example B2-1.

[0991] [Comparative Example B2-1]

[0992] The laminate produced in Comparative Example B1-1 was placed in an inert gas oven and subjected to a heat treatment under the same conditions as in Example B2-1.

[0993] The appearances of the laminates subjected to the heat treatment in Examples B2-1 to B2-5 and Comparative Example B2-1 were visually observed to confirm whether voids or delamination occurred, and the heat resistance was evaluated. When no voids or delamination occurred, it was judged that the heat resistance was good. The results are shown in Table 4.

[0994] [Table 4]

[0995]

[0996] [B6]Evaluation of peelability

[0997] [Example B3-1]

[0998] For the laminate that has been post-heat treated in Example B2-1, using a laser irradiation device, the adhesive layer was irradiated with laser light with a wavelength of 308 nm from the glass wafer side at 200 mJ / cm 2 The lowest irradiation dose at which peeling occurred was taken as the optimum irradiation dose. Then, the entire surface of the adhesive layer was irradiated with laser light with a wavelength of 308 nm at the optimum irradiation dose from the glass wafer side of the laminate, and the support substrate was manually lifted to confirm whether peeling was possible. The case where peeling was possible was designated as "possible", and the case where peeling was not possible was designated as "not possible". The results are shown in Table 5.

[0999] [Examples B3-2 to B3-5]

[1000] Using the laminates that had been post-heat treated in Examples B2-2 to B2-5, evaluation was carried out in the same manner as in Example B3-1 except for this. The results are shown in Table 5.

[1001] [Comparative Example B3-1]

[1002] Using the laminate that had been post-heat treated in Comparative Example B2-1, evaluation was carried out in the same manner as in Example B3-1 except for this. The results are shown in Table 5.

[1003] [Table 5]

[1004]

[1005] [B7]Evaluation of cleanability

[1006] [Example B4-1]

[1007] A 12-inch bare silicon wafer obtained in Example B3-1 was pasted onto a dicing tape (manufactured by Nitto Denko Corporation, DU-300) and fixed. The silicon wafer fixed with the dicing tape was cut into 4×4 cm using a dicing machine for singulation. The singulated silicon wafer was immersed in 7 mL of the cleaning agent composition prepared in Preparation Example B1 for 5 minutes, dried with an air gun, and the removability (cleanability) of the adhesive layer was investigated. The surface of the silicon wafer was observed using an optical microscope, and the case where no residue after laser irradiation was observed was designated as "possible", and the case where residue was observed was designated as "not possible". The results are shown in Table 6.

[1008] [Examples B4-2 to B4-5]

[1009] Using the 12-inch bare silicon wafers obtained in Examples B3-2 to B3-5, except for this, the evaluation was carried out in the same manner as in Example B4-1. The results are shown in Table 6. It should be noted that in Comparative Example B3-1, the adhesive layer could not be peeled off, so this evaluation was not carried out.

[1010] [Table 6]

[1011]

[1012] Description of reference numerals

[1013] 1: Semiconductor substrate; 2: Adhesive layer; 2a: Adhesive coating layer; 3: Release agent layer; 4: Support substrate; 21: Semiconductor chip substrate; 22: Adhesive layer; 22': Adhesive coating layer; 23: Release agent layer; 24: Support substrate; 25: Sealing resin; 26: Electronic device layer; 27: Release agent layer having adhesive properties; 28: Wiring layer.

Claims

1. A stripping agent composition or an adhesive composition, which is a stripping agent composition for photoirradiation stripping or an adhesive composition for photoirradiation stripping, The stripping agent composition or the adhesive composition contains: A novolak resin having at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, An epoxy resin containing a siloxane skeleton, and A solvent.

2. The stripping agent composition or the adhesive composition according to claim 1, wherein The novolak resin contains at least any one of a structural unit represented by the following formula (C1-1), a structural unit represented by the following formula (C1-2), and a structural unit represented by the following formula (C1-3), In the formula, C 1 represents a group derived from an aromatic compound containing a nitrogen atom, C 2 represents a group containing a tertiary carbon atom or a quaternary carbon atom in which the side chain has at least one selected from the group consisting of a secondary carbon atom, a quaternary carbon atom, and an aromatic ring; or represents a methylene group, C 3 represents a group derived from an aliphatic polycyclic compound C 4 represents a group derived from phenol, a group derived from bisphenol, a group derived from naphthol, a group derived from biphenyl or a group derived from biphenol, C 5 represents a single bond or a group having a structure derived from styrene, In formula (C1-1), C 1 , C 2 and C 5 at least any one of them has at least any group of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring. In formula (C1-2), C 1 , C 3 and C 5 each have at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring, In formula (C1-3), C 2 , C 4 and C 5 each have at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

3. The stripping agent composition or the adhesive composition according to claim 2, wherein The novolak resin contains at least any one of a structural unit represented by the following formula (C1-1-1) and a structural unit represented by the following formula (C1-1-2) as the structural unit represented by the formula (C1-1), In Formula (C1-1-1) and Formula (C1-1-2), R 901 and R 902 represent substituents substituted on the ring, each independently representing a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, R 903 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, R 904 represents a hydrogen atom, an optionally substituted aryl group or an optionally substituted heteroaryl group, R 905 represents an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted heteroaryl group, R 904 The group of 905 and the group of R are optionally bonded to each other to form a divalent group. Ar 901 and Ar 902 each independently represents an aromatic ring, X 1 and X 2 each independently represents a hydroxyl group or a carboxyl group, Z 1 represents a single bond or a group having a structure derived from styrene, h 1 and h 2 each independently represents an integer from 0 to 3, k 1 and k 2 each independently represents an integer from 0 to 3, h 1 and k 1 have a sum of 3 or less; h 2 and k 2 have a sum of 3 or less, n represents an integer of 1 or 2, Among them, the structural unit represented by the formula (C1-1-1) and the structural unit represented by the formula (C1-1-2) each independently have at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

4. The stripping agent composition or the adhesive composition according to claim 2, wherein The novolak resin contains a structural unit represented by the following formula (C1-3-1) as the structural unit represented by the formula (C1-3), In formula (C1-3-1), R 801 represents a substituent substituted on the ring, and each independently represents a halogen atom, a nitro group, a cyano group, an amino group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, R 802 represents a hydrogen atom, an optionally substituted aryl or an optionally substituted heteroaryl, R 803 represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, R 802 The group of 803 and the group of R are optionally bonded to each other to form a divalent group. Ar 801 represents a benzene ring, a naphthalene ring or a biphenyl structure, X 11 represents a hydroxyl group or a carboxyl group, Z 1 represents a single bond or a group having a structure derived from styrene, h 11 each independently represents an integer from 0 to 4 k 11 each independently represents an integer from 0 to 4 Ar 801 When Ar is a benzene ring, h 11 and k 11 have a total of 4 or less. When Ar 801 is a naphthalene ring, h 11 and k 11 have a total of 6 or less. When Ar 801 is a biphenyl structure, h 11 and k 11 have a total of 8 or less. Among them, the structural unit represented by the formula (C1-3-1) has at least any one of a hydroxyl group directly bonded to an aromatic ring and a carboxyl group directly bonded to an aromatic ring.

5. The stripping agent composition or the adhesive composition according to claim 1, wherein The epoxy resin containing a siloxane skeleton contains the structure represented by the following formula (A), In formula (A), R 1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R 2 represents an alkylene group having 1 to 10 carbon atoms; Y represents a single bond or -O-; Ep represents a group represented by the following formula (A-1) or formula (A-2); * represents a bonding bond, In the formula (A-1) and the formula (A-2), * represents a bonding bond.

6. The stripping agent composition or the adhesive composition according to claim 1, wherein The epoxy resin containing a siloxane skeleton is represented by any one of the following formulas (SE1) to (SE3) In formula (SE1), R 101 ~R 110 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; X 101 represents a group represented by the following formula (EA); Y 101 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms, where it is different from X 101 ; l represents an integer of 0 or more; m represents an integer of 1 or more; n represents an integer of 0 or more, In formula (SE2), R 201 ~R 207 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; X 201 and X 202 each independently represents a group represented by the following formula (EA); Y 201 represents a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 30 carbon atoms; l represents an integer of 0 or more; m represents an integer of 0 or more, In formula (SE3), R 301 ~R 304 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; X 301 ~X 304 each independently represents a group represented by the following formula (EA); m represents an integer of 1 to 3, In formula (EA), R 2 represents an alkylene group having 1 to 10 carbon atoms; Y represents a single bond or -O-; Ep represents a group represented by the following formula (A-1) or formula (A-2); * represents a bonding bond, In the formula (A-1) and the formula (A-2), * represents a bonding bond.

7. The stripping agent composition or the adhesive composition according to claim 1, wherein The content of the epoxy resin containing a siloxane skeleton is 5% by mass to 40% by mass with respect to the novolak resin.

8. A laminate, wherein, Having: a semiconductor substrate or an electronic device layer, a light-transmissive support substrate, and a stripping agent layer provided between the semiconductor substrate or the electronic device layer and the support substrate, The stripping agent layer is a stripping agent layer formed from the stripping agent composition according to any one of claims 1 to 7.

9. The laminate according to claim 8, wherein The laminate has: an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate.

10. A method for manufacturing a processed semiconductor substrate or an electronic device layer, wherein, Including: A 5A process of processing the semiconductor substrate of the laminate according to claim 8; Or a fifth B step of processing the electronic device layer of the laminate according to claim 8; And A sixth A step of separating the semiconductor substrate processed by the fifth A step from the support substrate; or a sixth B step of separating the electronic device layer processed by the fifth B step from the support substrate.

11. The method for manufacturing a processed semiconductor substrate or electronic device layer according to claim 10, wherein The sixth A step or the sixth B step includes a step of irradiating the laminate with a laser from the support substrate side.

12. A laminate, wherein, Comprising: a semiconductor substrate or an electronic device layer, a light-transmissive support substrate, and an adhesive layer provided between the semiconductor substrate or the electronic device layer and the support substrate, The adhesive layer is an adhesive layer formed of the adhesive composition according to any one of claims 1 to 7.

13. A method for manufacturing a processed semiconductor substrate or an electronic device layer, wherein, Including: A fifth A step of processing the semiconductor substrate of the laminate according to claim 12; Or a fifth B step of processing the electronic device layer of the laminate according to claim 12; And A sixth A step of separating the semiconductor substrate processed by the fifth A step from the support substrate; or a sixth B step of separating the electronic device layer processed by the fifth B step from the support substrate.

14. The method for manufacturing a processed semiconductor substrate or electronic device layer according to claim 13, wherein The sixth A step or the sixth B step includes a step of irradiating the laminate with a laser from the support substrate side.

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